Catalyst for hydrosilylation reaction, hydrogenation reaction, and hydrosilane reduction reaction

ABSTRACT

Provided is a catalyst which comprises a compound represented by formula (1) and which exhibits activity for at least one type of reaction selected from among hydrosilylation reaction or hydrogenation reaction with respect to an aliphatic unsaturated bond and hydrosilane reduction reaction with respect to a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond. Formula (1): Mn(Lm) {M represents Fe, Co, or Ni having an oxidation number of 0, L represents an isocyanide ligand represented by formula (2), n denotes an integer of 1-8, and m denotes an integer of 2-12. Formula (2): (CN)x—R1 (R1 represents a mono- to trivalent-organic group having 1-30 carbon atoms, optionally being substituted by a halogen atom, and optionally having interposed therein one or more atoms selected from among O, N, S, and Si; and x denotes an integer of 1-3)}.

TECHNICAL FIELD

The present invention relates to a catalyst made of a prescribedmetal-isocyanide complex, and relates more specifically to a catalysthaving activity in at least one reaction selected from hydrosilylationreaction or hydrogenation reaction on an aliphatic unsaturated bond andhydrosilane reduction reaction on a carbon-oxygen unsaturated bond or acarbon-nitrogen unsaturated bond.

BACKGROUND ART

Hydrosilylation reaction which is addition of a Si—H functional compoundto a compound having a carbon-carbon double bond or triple bond is auseful method for the synthesis of organosilicon compounds and anindustrially important synthesis reaction.

As the catalyst for hydrosilylation reaction, Pt, Pd and Rh compoundsare known. Among others, Pt compounds as typified by Speier's catalystand Karstedt's catalyst are most commonly used.

While several problems arise with reaction in the presence of Ptcompounds as the catalyst, one problem is that upon addition of a Si—Hfunctional compound to terminal olefin, a side reaction due to internalrearrangement of olefin takes place. Since this system does not exertaddition reactivity to the internal olefin, unreacted olefin is left inthe addition product. To drive the reaction to completion, it isnecessary to use an excess amount of olefin in advance by taking intoaccount the left by the side reaction.

Another problem is that the selectivity of α- and β-adducts is lowdepending on the type of olefin.

The most serious problem is that all the center metals Pt, Pd and Rh arequite expensive noble metal elements. As metal compound catalysts whichcan be used at lower cost are desired, a number of research works havebeen made thereon.

For example, reaction in the presence of iron-carbonyl complexes(Fe(CO)₅, Fe₃(CO)₁₂) is known from Non-Patent Document 1, although thisreaction requires reaction conditions including as high a temperature as160° C. or photo-irradiation (Non-Patent Document 2).

For these iron-carbonyl complexes, it is reported in Non-Patent Document3 and Patent Document 1 that products formed by dehydrogenativesilylation are obtained rather than the addition reaction.

Also, Non-Patent Document 4 and Patent Document 2 report a reaction ofmethylvinyldisiloxane and methylhydrogendisiloxane in the presence of aniron-carbonyl complex coordinated with a cyclopentadienyl group. Sincedehydrogenative silylation reaction takes place along with the relevantreaction, the selectivity of addition reaction is low.

Non-Patent Document 5 refers to reaction in the presence of an ironcatalyst having a terpyridine ligand. Although PhSiH₃ and Ph₂SiH₂ add toolefins, more useful trialkylsilanes, alkoxysilanes and siloxanes havepoor addition reactivity to olefins.

Non-Patent Document 6 reports that from reaction in the presence of aniron catalyst having a terpyridine ligand and a bistrimethylsilylmethylgroup, an addition reaction product is obtained in high yields. Thismethod needs a catalyst synthesis, including first synthesizing aterpyridine-iron complex as a catalyst precursor and introducing abistrimethylsilylmethyl group therein at a low temperature, which is noteasy.

Also, Non-Patent Documents 7 and 8 report iron complexes having abisiminopyridine ligand. It is disclosed that they exhibit highreactivity to alkoxysilanes and siloxanes under mild conditions.

However, at the time of the synthesis of this complex, there are pointsat issue such as using Na amalgam, which consists of water-sensitivesodium and highly toxic mercury and needs care in handling (or usingwater-sensitive NaBEt₃H), and the storage requiring the conditions ofbeing at low temperature in an inert-gas nitrogen atmosphere because ofthe low stability of the complex compound itself.

Also an iron complex having a chiral iminopyridine oxazoline ligand isreported (Non-Patent Document 9), and the report shows an example ofreaction between a tertiary alkene and Ph₂SiH₂. However, a reducingagent (NaBHEt₃) is needed, and dihydrodiphenylsilane is not a reactionsubstrate having high industrial value.

Also an example of reaction by a cobalt-carbonyl complex (Co₂(CO)₈ orthe like) is reported (Non-Patent Documents 10 to 15); however, this isnot satisfactory in terms of reaction yield or reaction molar ratio, andthe complex has highly toxic carbon monoxide and the handling andstorage of the complex require the conditions of being in an inert gasatmosphere and at low temperature.

Also an example of reaction of olefin with trialkylsilane in thepresence of a cobalt-carbonyl complex having a trialkylsilyl group isreported in Non-Patent Document 16, but the yield is low and theselectivity is low.

Non-Patent Document 17 reports reaction of olefin with trialkylsilane inthe presence of a cobalt-phosphite complex coordinated with acyclopentadienyl group, and Non-Patent Document 18 reports reaction ofolefin with trihydrophenylsilane in the presence of a cobalt complexcoordinated with N-heterocyclic carbene. Because of low stability, thesecomplex compounds require an inert gas atmosphere and a low temperaturefor handling and storage.

Also an example of reaction by a cobalt catalyst having a β-diketiminategroup as a ligand is reported (Non-Patent Document 19); however, whenthe reaction substrate is trihydrophenylsilane, the industrial utilityvalue is low. Although also an example of reaction between 1-hexene andtriethoxysilane is shown, the amount of the catalyst needs to be 2 mol%, and the catalytic activity is not high.

Also an example of reaction by a cobalt catalyst having apyridinediimine ligand, the precursor of which catalyst is easy tohandle, is reported, and the catalyst has high catalytic activity(Non-Patent Document 20); however, in this reaction, alsodehydrogenative silylation reaction progresses, and therefore minuteamounts of dehydrogenative silylated compounds always coexist;consequently, the selectivity of the addition product is low.

Also a hydrosilylation reaction catalyst usingbis(cyclooctatetraenyl)iron and an isocyanide compound as ligands(Non-Patent Document 21) and a hydrosilylation reaction catalyst usingiron pivalate or cobalt pivalate and an isocyanide compound as ligands(Non-Patent Document 22) are reported; however, neither is comparable toPt catalysts in terms of catalytic activity, and the development of acatalyst having higher catalytic activity is desired.

Further, in hydrosilylation reaction using an alkenyl sulfide derivativeas an unsaturated compound, the sulfur element acts as a catalyticpoison; hence, an example using a Pt catalyst and an example using a Rhcatalyst, which are only among few examples of reports, are reported(Non-Patent Documents 23 and 24). However, the catalytic activity islower than in other substrates, and the selectivity of the additionreaction product is low.

The example using a Rh catalyst reports that an addition product inwhich Si is bonded to carbon adjacent to the sulfur element is obtainedselectively (Non-Patent Document 25); however, the catalytic activity islow, and the selectivity of the adduct is low.

Many examples of the nickel complex catalyst are reported. For example,a catalyst having a phosphine ligand (Non-Patent Document 26) lacks inselectivity and requires careful handling and storage.

With a vinylsiloxane-coordinated catalyst (Non-Patent Document 27), aproduct due to the dehydrogenative becomes predominant, indicating lowselectivity of addition reaction.

With an allylphosphine-coordinated catalyst (Non-Patent Document 28),the yield is low, and trihydrophenylsilane is not a reaction substrateof industrial worth.

A metal bisamide catalyst (Non-Patent Document 29) needs carefulhandling and storage, and dihydrodiphenylsilane is not a reactionsubstrate of industrial worth.

A catalyst having N-heterocyclocarbene ligand (Non-Patent Document 30)has low selectivity of reaction, and trihydrophenylsilane is not ofindustrial worth.

Also Patent Documents 3 to 6 report iron, cobalt and nickel catalystshaving terpyridine, bisiminopyridine and bisiminoquinoline ligands. Likethe above-cited Non-Patent Documents 6 to 8, there is an industrialdifficulty of synthesis of a catalyst precursor or synthesis of thecomplex catalyst from the precursor.

Patent Document 7 discloses a method of conducting reaction in thepresence of a complex catalyst having a bisiminoquinoline ligand, usingMg(butadiene).2THF or NaEt₃BH as the catalyst activator. Likewise, theyield of the desired product is less than satisfactory.

The catalysts with their application to organopolysiloxanes being bornein mind include a catalyst having a phosphine ligand (Patent Document8), a catalyst having an aryl-alkyl-triazenide group (Patent Document9), a colloidal catalyst (Patent Document 10), a catalyst coordinatedwith a sulfide group (Patent Document 11), and a catalyst coordinatedwith an amino, phosphino or sulfide group and an organosiloxane group(Patent Document 12).

However, reactivity is empirically demonstrated with respect to onlyplatinum, palladium, rhodium and iridium which are expensive metalelements. Thus the method is not regarded cost effective.

In Examples of Patent Documents 13 and 14, only well-known platinumcatalysts are demonstrated to exert a catalytic effect while thestructure which is combined with another metal to exert catalyticactivity is indicated nowhere.

Patent Documents 15 to 17 disclose catalysts coordinated with carbene.Patent Document 15 does not discuss whether or not the catalyst iseffective to hydrosilylation reaction.

Patent Documents 16 and 17 disclose catalysts coordinated with carbeneand vinylsiloxane, but describe only platinum catalysts in Examples.

In addition, the metal catalysts coordinated with carbene requirecareful handling because the complex compounds have low storagestability.

Patent Documents 18 to 24 disclose a method of mixing a metal salt witha compound which coordinates to the metal and using the product as acatalyst rather than the use of metal complexes as the catalyst.Although these Patent Documents describe the progress of hydrosilylationwith several exemplary combinations, the yield and other data aredescribed nowhere, and the extent to which the reaction takes place isnot evident. In addition, ionic salts or hydride reducing agents areused as the activator in all examples. Nevertheless, almost all examplesexhibit no catalytic activity.

On the other hand, there are also many reports on hydrogenation reactionin which a hydrogen molecule is added to an olefin, which is a compoundhaving a carbon-carbon double bond. For example, hydrogenation bythermal reaction using Fe(CO)₅ as a catalyst (Non-Patent Document 31)and hydrogenation by photoreaction (Non-Patent Document 32) arereported. However, thermal reaction requires conditions of hightemperature and high pressure (180° C., 28 atmospheres); in contrast,photoreaction progresses at room temperature; but both have low turnovernumbers (TON), which number indicates the number of revolutions of thecatalyst, and cannot be said to have sufficient activity.

Further, an example of reaction using an iron catalyst using an organicaluminum compound as a reaction aid (Non-Patent Document 33) and anexample of reaction using a Grignard compound or a lithium aluminumhydride compound and an iron chloride catalyst in combination(Non-Patent Documents 34 and 35) are reported; however, the TON is lessthan or equal to 20, and the catalytic activity is low.

Also an iron catalyst having a phosphorus-based compound as a ligand isreported (Non-Patent Document 36); in this system, although reaction ismade under conditions of room temperature and relatively low pressure (4atmospheres), the turnover number cannot be said to be sufficient.

Also an example of an iron catalyst having a1,2-bis(dimethylsilyl)benzene ligand is reported (Non-Patent Document37); in this example, although reaction progresses at room temperatureunder normal pressure, the synthesis of the catalyst is not easy.

Also an example of an iron catalyst having a bis(imino)pyridine ligandis reported (Non-Patent Document 7), and this example has goodreactivity, i.e., a TON of 1,814, under conditions of room temperatureand relatively low pressure (4 atmospheres).

Further, an iron catalyst having a2,6-bis(arylimidazol-2-ylidene)pyridine ligand is reported (Non-PatentDocument 38); however, both have points at issue such as safety at thetime of synthesis and the stability of the compound, similarly to the Fecomplex having a bis(imino)pyridine ligand mentioned above.

Also a cobalt catalyst having a phosphorus-based compound as a ligand isreported (Non-Patent Document 39); in this system, although reactionprogresses at room temperature under normal pressure, the synthesis ofthe catalyst is not easy.

A cobalt catalyst having a bis(mesitylbenzimidazol-2-ylidene)phenylligand is reported (Non-Patent Document 40); however, this has points atissue such as safety at the time of synthesis and the stability of thecompound, similarly to the Fe complex having a2,6-bis(arylimidazol-2-ylidene)pyridine ligand mentioned above, andfurthermore the catalytic activity cannot be said to be sufficient, inview of the TON being 50.

Further, as methods for reducing compounds having a carbon-oxygen orcarbon-nitrogen double bond and a carbon-nitrogen triple bond, there isa method in which hydrogen is used in the presence of a hydrogencompound of aluminum or boron or a noble metal catalyst. Among carbonylcompounds, for ketones and aldehydes, a stable, easy-to-handle hydridereaction agent and a noble metal catalyst for hydrogenation that allowreaction to progress under mild conditions are known; on the other hand,for the reduction of carboxylic acid derivatives such as esters andamides, a method using a strong reducing agent such as lithium aluminumhydride or a borane is mainly used (Non-Patent Document 41). However,these reducing agents are ignitable, water-sensitive substances, and aretherefore less easy to handle. Further, care is required in handlingalso when removing aluminum or a boron compound after reaction from thedesired product.

A large number of methods in which a hydrosilane compound or methylhydrogen polysiloxane, which is stable and easy to handle in air, isused as a reducing agent are reported; however, the reaction requiresthe addition of a strong acid or a Lewis acid, or the use of anexpensive noble metal catalyst. These days, hydrosilane reductionreactions of a carbonyl compound using inexpensive iron, cobalt, ornickel as a catalyst are reported; some examples of them are used forreduction reaction of an amide, for which conventional methods needsevere conditions. Specific examples include Non-Patent Documents 37,and 42 to 49; however, a highly active catalyst exhibiting a higherturnover number is desired.

On the other hand, an iron-, cobalt-, or nickel-isocyanide complex isknown in Non-Patent Documents 50 to 62; however, these literatures aremainly for the synthesis, structure analysis, and reaction of thecomplex, and have no example in which the complex is used as a catalystfor hydrosilylation reaction or hydrogenation reaction on an aliphaticunsaturated bond or hydrosilane reduction reaction on a carbon-oxygenunsaturated bond or a carbon-nitrogen unsaturated bond.

PRIOR ART DOCUMENTS Patent Documents

-   Patent Document 1: WO 2013/081794-   Patent Document 2: WO 2010/016416-   Patent Document 3: JP-A 2012-532885-   Patent Document 4: JP-A 2012-532884-   Patent Document 5: JP-A 2013-544824-   Patent Document 6: JP-A 2014-502271-   Patent Document 7: JP-A 2014-503507-   Patent Document 8: JP-A H06-136126-   Patent Document 9: JP-A H06-263780-   Patent Document 10: JP-A H01-315344-   Patent Document 11: JP 3174616-   Patent Document 12: JP-A H07-149780-   Patent Document 13: JP-A 2001-131231-   Patent Document 14: JP 4007467-   Patent Document 15: JP 3599669-   Patent Document 16: JP 3854151-   Patent Document 17: JP 4249702-   Patent Document 18: WO 2013/043846-   Patent Document 19: WO 2013/043783-   Patent Document 20: WO 2013/043912-   Patent Document 21: WO 2014/021908-   Patent Document 22: WO 2013/081794-   Patent Document 23: WO 2013/043785-   Patent Document 24: WO 2013/043787

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SUMMARY OF INVENTION Technical Problem

The present invention has been made in view of such circumstances, andan object of the present invention is to provide a catalyst that canexhibit excellent catalytic activity in hydrosilylation reaction orhydrogenation reaction on an aliphatic unsaturated bond or hydrosilanereduction reaction on a carbon-oxygen unsaturated bond or acarbon-nitrogen unsaturated bond, and a method for producing variouscompounds using the catalyst.

Solution to Problem

The present inventors conducted extensive studies in order to achievethe object mentioned above, and have found out that a prescribed iron-,cobalt-, or nickel-isocyanide complex can exhibit excellent catalyticactivity in hydrosilylation reaction or hydrogenation reaction on analiphatic unsaturated bond or hydrosilane reduction reaction on acarbon-oxygen unsaturated bond or a carbon-nitrogen unsaturated bond,and allows each of the reactions mentioned above to progress under mildconditions; thus, have completed the present invention.

The invention provides a catalyst and a method defined below.

1. A catalyst including a compound represented by formula (1) below, andhaving activity in at least one reaction selected from hydrosilylationreaction or hydrogenation reaction on an aliphatic unsaturated bond andhydrosilane reduction reaction on a carbon-oxygen unsaturated bond or acarbon-nitrogen unsaturated bond,

M_(n)(L)_(m)  (1)

wherein M represents Fe, Co, or Ni with an oxidation number of 0, Lrepresents an isocyanide ligand represented by formula (2) below, nrepresents an integer of 1 to 8, and m represents an integer of 2 to 12,

(CN)_(x)—R¹  (2)

wherein R¹ represents a monovalent to trivalent organic group that has 1to 30 carbon atoms and is optionally substituted with a halogen atom andin which one or more atoms selected from oxygen, nitrogen, sulfur, andsilicon are optionally interposed, and x represents an integer of 1 to3.2. The catalyst according to 1, wherein, in the formula (2), x is 1.3. The catalyst according to 1 or 2, wherein, in the formula (1), whenn=1, m=2, 4, or 5, and when n=2 to 4, m=an integer of 6 to 10.4. The catalyst according to any one of 1 to 3, wherein, in the formula(1), when M is Fe, n=1 and m=5, when M is Co, n=2 and m=8, and when M isNi, n=1 and m=2 or 4, or n=3, 4, or 8 and m=4, 6, 7, or 12.5. The catalyst according to any one of 1 to 4, wherein M in the formula(1) is Fe or Co.6. The catalyst according to any one of 1 to 5, wherein R¹ in theformula (2) is a monovalent hydrocarbon group having 1 to 30 carbonatoms.7. The catalyst according to 6, wherein R¹ in the formula (2) is atleast one hydrocarbon group selected from an alkyl group having 1 to 20carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an arylgroup having 6 to 30 carbon atoms, and an alkylaryl group having 7 to 30carbon atoms.8. The catalyst according to 7, wherein R¹ in the formula (2) is atleast one hydrocarbon group selected from a t-butyl group, a 1-adamantylgroup, a mesityl group, a phenyl group, a 2,6-dimethylphenyl group, anda 2,6-diisopropylphenyl group.9. A method for producing a product of hydrosilylation reaction betweenan aliphatic unsaturated bond-containing compound and a Si—Hbond-containing compound, wherein the method uses the catalyst accordingto any one of 1 to 8.10. A method for producing a product of hydrogenation reaction of analiphatic unsaturated bond-containing compound, wherein the method usesthe catalyst according to any one of 1 to 8.11. The production method according to 9 or 10, wherein the aliphaticunsaturated bond-containing compound is an olefin compound, or a silanecompound or an organopolysiloxane having an alkenyl group bonded to a Siatom.12. A method for producing a product of reduction reaction by a Si—Hbond-containing compound of a compound having a carbon-oxygenunsaturated bond or a carbon-nitrogen unsaturated bond, wherein themethod uses the catalyst according to any one of 1 to 8.13. The method for producing a product of reduction reaction accordingto 12, wherein the compound having a carbon-oxygen unsaturated bond or acarbon-nitrogen unsaturated bond is an aldehyde compound, a ketonecompound, an amide compound, or a nitrile compound.

Advantageous Effects of Invention

A catalyst for reaction made of an iron-, cobalt-, or nickel-isocyanidecomplex (hereinafter, simply abbreviated as an isocyanide complex) ofthe present invention does not have a carbonyl ligand highly toxic tohuman bodies, and has high thermal stability and high stability in airof the complex.

When the isocyanide complex of the present invention is used as acatalyst to perform hydrosilylation reaction between an aliphaticunsaturated bond-containing compound and a silane or a (poly)siloxanehaving a Si—H group, addition reaction can be made under conditions ofroom temperature to less than or equal to 100° C. In particular, alsoaddition reaction with an industrially useful (poly)siloxane, atrialkoxysilane, or a dialkoxysilane progresses well. A known literatureshows that, in the same reaction, both addition reaction on anunsaturated bond and reaction that produces an unsaturatedbond-containing compound due to dehydrogenative silylation reactionprogress simultaneously in many cases; in contrast, when the catalyst ofthe present invention is used, addition reaction on an unsaturated bondprogresses selectively.

In addition, in reaction with an internal olefin, which has beendifficult for conventional catalysts, a product of addition reactionaccompanied by movement of an unsaturated bond to an end can beobtained.

Further, by using the catalyst of the present invention, inhydrosilylation reaction of an alkenyl sulfide or the like, an additionproduct in which Si is bonded to carbon adjacent to the sulfur elementis obtained selectively.

Further, the catalyst of the present invention has high catalyticactivity on hydrogenation reaction of an aliphatic unsaturatedbond-containing compound, and the reaction progresses under mildconditions.

Further, in hydrosilane reduction reaction on a carbon-oxygenunsaturated bond or a carbon-nitrogen unsaturated bond using thecatalyst of the present invention, a carbonyl compound such as an amidecompound, a ketone compound, or an amide compound, or a nitrilecompound, and an easy-to-handle silane or (poly)siloxane having a Si—Hgroup are reacted together, and the desired compound can be obtainedwith a high yield.

Thus, the catalyst made of an isocyanide complex of the presentinvention has activity on one or a plurality of reactions amonghydrosilylation reaction or hydrogenation reaction on an aliphaticunsaturated bond and hydrosilane reduction reaction on a carbon-oxygenunsaturated bond or a carbon-nitrogen unsaturated bond, and is thereforevery highly useful in organic synthesis reaction.

DESCRIPTION OF EMBODIMENTS

Below the invention is described in more detail.

The invention provides a catalyst including a compound represented byformula (1) below, and having activity in at least one reaction selectedfrom hydrosilylation reaction or hydrogenation reaction on an aliphaticunsaturated bond and hydrosilane reduction reaction on a carbon-oxygenunsaturated bond or a carbon-nitrogen unsaturated bond.

M_(n)(L)_(m)  (1)

In formula (1), M represents Fe, Co, or Ni with an oxidation number of0, L represents an isocyanide ligand represented by formula (2) below, nrepresents an integer of 1 to 8, and m represents an integer of 2 to 12.

(CN)_(x)—R¹  (2)

In formula (1), as mentioned above, n represents 1 to 4, and mrepresents 2 to 10; from the viewpoints of the stability of the complexand catalytic activity, it is preferable that, in the case where n is 1,m be 2, 4, or 5; in the case where n=2 to 4, m be an integer of 6 to 10;in the case where n=8, m be 12; it is more preferable that, in the casewhere M is Fe, n be 1 and m be 5; in the case where M is Co, n be 2 andm be 8; in the case where M is Ni, n be 1 and m be 2 or 4, or n be 3, 4,or 8 and m be 4, 6, 7, or 12.

In formula (2), R¹ represents a monovalent to trivalent organic groupthat has 1 to 30 carbon atoms and is optionally substituted with ahalogen atom and in which one or more atoms selected from oxygen,nitrogen, sulfur, and silicon are optionally interposed, and xrepresents an integer of 1 to 3.

Specific examples of the halogen atom include fluorine, chlorine,bromine, and iodine.

The monovalent to trivalent organic group having 1 to 30 carbon atoms isnot particularly limited, but is preferably a monovalent to trivalenthydrocarbon group having 1 to 30 carbon atoms.

Examples of monovalent hydrocarbon groups include alkyl, alkenyl,alkynyl, aryl, alkyl aryl, and aralkyl groups.

The alkyl groups may be straight, branched or cyclic, is preferably 1 to20, more preferably 1 to 10 alkyl group. Examples include straight orbranched alkyl groups such as methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl,n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl,n-octadecyl, n-nonadecyl, and n-eicosanyl; and cycloalkyl groups such ascyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, norbornyl, and adamantyl.

The alkenyl group is preferably an alkenyl group having 2 to 20 carbonatoms, and examples include ethenyl, n-1-propenyl, n-2-propenyl,1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl,2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, andn-1-eicosenyl.

The alkynyl group is preferably an alkynyl group having 2 to 20 carbonatoms, and examples include ethynyl, n-1-propynyl, n-2-propynyl,n-1-butynyl, n-2-butynyl, n-3-butynyl, 1-methyl-2-propynyl,n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl,1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n-butynyl,1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n-1-pentadecynyl, andn-1-eicosynyl.

The aryl or alkylaryl group is preferably an aryl group having 6 to 20carbon atoms or an alkylaryl group having 7 to 20 carbon atoms, andspecific examples include phenyl, 1-naphthyl, 2-naphthyl, anthryl,phenanthryl, o-biphenylyl, m-biphenylyl, p-biphenylyl, tolyl,2,6-dimethylphenyl, 2,6-diisopropylphenyl, a mesityl group, and thelike.

The aralkyl group is an arylalkyl group preferably having 7 to 30 carbonatoms and more preferably having 7 to 20 carbon atoms, and specificexamples include benzyl, phenylethyl, phenylpropyl, naphthylmethyl,naphthylethyl, a naphthylpropyl group, and the like.

Suitable divalent hydrocarbon groups include alkylene, arylene andaralkylene groups.

The alkylene groups may be straight, branched or cyclic ones, preferablyalkylene groups having 1 to 20 carbon atoms. Examples include straightor branched alkylene groups such as methylene, ethylene, propylene,trimethylene, n-butylene, isobutylene, s-butylene, n-octylene,2-ethylhexylene, n-decylene, n-undecylene, n-dodecylene, n-tridecylene,n-tetradecylene, n-pentadecylene, n-hexadecylene, n-heptadecylene,n-octadecylene, n-nonadecylene, and n-eicosanylene; and cycloalkylenegroups such as 1,4-cyclohexylene.

Examples of the arylene group include o-phenylene, m-phenylene,p-phenylene, 1,2-naphthylene, 1,8-naphthylene, 2,3-naphthylene, and4,4′-biphenylene.

Examples of the aralkylene group include —(CH₂)_(y)—Ar— wherein Ar is anarylene group having 6 to 20 carbon atom and y is an integer of 1 to 10,—Ar—(CH₂)_(y)— wherein Ar and y are as defined above, and—(CH₂)_(y)—Ar—(CH₂)_(y)— wherein Ar is as defined above and y is eachindependently as defined above.

Specific examples of the trivalent hydrocarbon group include thoserepresented by the following formulae, but are not limited to these.

Specific examples of other organic groups in R¹ above include alkoxygroups such as a methoxy group, an ethoxy group, a propoxy group, and anisopropoxy group; aryloxy groups such as a phenoxy group; alkyl halidegroups such as a trifluoromethyl group; alkylamino groups such as adimethylamino group; ester groups such as a methyl ester and an ethylester; a nitro group; a nitrile group; alkyl- or arylsilyl groups suchas a trimethylsilyl group and a phenyldimethylsilyl group; alkoxysilylgroups such as a trimethoxysilyl group, a triethoxysilyl group, adimethoxymethylsilyl group, and a diethoxymethylsilyl group;nitrogen-containing heterocycle-containing groups such as a pyridylgroup; sulfur-containing heterocycle-containing groups such as a thienylgroup; and the like.

Among these, R¹ is preferably at least one hydrocarbon group selectedfrom an alkyl group having 1 to 20 carbon atoms, a cycloalkyl grouphaving 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms,and an alkylaryl group having 7 to 30 carbon atoms, and is morepreferably a t-butyl group, a 1-adamantyl group, a mesityl group, aphenyl group, a 2,6-dimethylphenyl group, and a 2,6-diisopropylphenylgroup.

One or more atoms selected from oxygen, nitrogen, silicon, sulfur, andphosphorus may be interposed in each of the organic groups describedabove, and each of the organic groups described above may be substitutedwith a halogen atom.

x in formula (2) above represents an integer of 1 to 3, and ispreferably 1 or 2 and more preferably 1.

The isocyanide compound represented by formula (2) above may be obtainedas a commercially available product, or may be synthesized by a knownmethod. For example, it may be obtained by a method in which aformylated product is obtained from an amine compound and formic acid,and subsequently the formylated product is reacted with phosphorylchloride in the presence of an organic amine to be turned into anisocyanide (Synthesis Method 1; see Organometallics, 2004, 23,3976-3981); as a method for obtaining a formylated product under mildconditions, a formylated product can be obtained by forming aceticformic anhydride from acetic anhydride and formic acid, and reacting theacetic formic anhydride with an amine compound (Synthesis Method 2; seeOrg. Synth., 2013, 90, 358-366). The obtained formylated product can beturned into an isocyanide by the method described in Synthesis Method 1,which is the same as above.

The synthesis can be made also by a method in which an amine compoundand dichlorocarbene are reacted together to produce an isocyanide, whichis a method not involving formylation (Synthesis Method 3; seeTetrahedron Letters, 1972, 17, 1637-1640).

Examples of the isocyanide compound include alkyl isocyanides such asmethyl isocyanide, ethyl isocyanide, n-propyl isocyanide, cyclopropylisocyanide, n-butyl isocyanide, isobutyl isocyanide, sec-butylisocyanide, t-butyl isocyanide, n-pentyl isocyanide, isopentylisocyanide, neopentyl isocyanide, n-hexyl isocyanide, cyclohexylisocyanide, cycloheptyl isocyanide, 1,1-dimethylhexyl isocyanide,1-adamantyl isocyanide, and 2-adamantyl isocyanide; aryl isocyanidessuch as phenyl isocyanide, 2-methylphenyl isocyanide, 4-methylphenylisocyanide, 2,4-dimethylphenyl isocyanide, 2,5-dimethylphenylisocyanide, 2,6-dimethylphenyl isocyanide, 2,4,6-trimethylphenylisocyanide, 2,4,6-tri-t-butylphenyl isocyanide, 2,6-diisopropylphenylisocyanide, 1-naphthyl isocyanide, 2-naphthyl isocyanide,2-methyl-1-naphthyl isocyanide; aralkyl isocyanides such as benzylisocyanide and phenylethyl isocyanide.

Examples of the diisocyanide compound include 1,2-diisocyanoethane,1,3-diisocyanopropane, 1,4-diisocyanobutane, 1,5-diisocyanopentane,1,6-diisocyanohexane, 1,8-diisocyanooctane, 1,12-diisocyanododecane,1,2-diisocyanocyclohexane, 1,3-diisocyanocyclohexane,1,4-diisocyanocyclohexane, 1,3-diisocyano-2,2-dimethylpropane,2,5-diisocyano-2,5-dimethylhexane, 1,2-bis(diisocyanoethoxy)ethane,1,2-diisocyanobenzene, 1,3-diisocyanobenzene, 1,4-diisocyanobenzene,1,1′-methylenebis(4-isocyanobenzene), 1,1′-oxybis(4-isocyanobenzene),3-(isocyanomethyl)benzyl isocyanide, 1,2-bis(2-isocyanophenoxy)ethane,bis(2-isocyanophenyl)phenyl phosphonate, bis(2-isocyanophenyl)isophthalate, bis(2-isocyanophenyl) succinate.

Examples of the triisocyanide compound include1,3-diisocyano-2-(isocyanomethyl)-2-methylpropane,1,5-diisocyano-3-(2-isocyanoethyl)pentane,1,7-diisocyano-4-(3-isocyanopropyl)heptane, and3-isocyano-N,N′-bis(3-isocyanopropyl)propane-1-amine.

A catalyst made of an isocyanide complex represented by formula (1)above can be synthesized by a known method; for example, the synthesiscan be made by a method in which an iron, cobalt, or nickel salt and areducing agent are reacted together in an organic solvent in thepresence of an isocyanide compound, or a method in which an iron-,cobalt-, or nickel-carbonyl complex and an isocyanide compound arereacted together in an organic solvent at high temperature under lightirradiation or in the presence of a catalyst. The synthesis can be madealso by reacting together an iron, cobalt, or nickel complex having asubstitutable ligand and an isocyanide compound in an organic solvent.

The synthesis can be made also by reacting together an ate-type iron-,cobalt-, or nickel-isocyanide complex and an oxidizing agent in anorganic solvent.

The iron, cobalt, or nickel salt mentioned above is not particularlylimited, but is preferably a halide of Cl, Br, I, or the like, or acarboxylate such as acetate, and is more preferably a halide of Cl, Br,I, or the like, in view of reactivity with a reducing agent.

Specific examples of the iron salt include iron halides such as FeCl₂,FeBr₂, FeCl₃, FeBr₃, and FeI₃; iron carboxylates such as Fe(OAc)₂,Fe(stearate)₂, and Fe(stearate)₃; and the like.

Specific examples of the cobalt salt include cobalt halides such asCoCl₂, CoBr₂, and CoI₂; cobalt carboxylates such as Co(OAc)₂, Co(OBz)₂,Co(2-ethylhexanoate)₂, and Co(stearate)₂; and the like.

Specific examples of the nickel salt include nickel halides such asNiCl₂, NiBr₂, and NiI₂; nickel carboxylates such as Ni(OAc)₂; and thelike.

Specific examples of the iron-, cobalt-, or nickel-carbonyl complexmentioned above include Fe(CO)₅, Fe₃(CO)₁₂, Co₂(CO)₈, Ni(CO)₄, and thelike.

As the substitutable ligand, olefin compounds such as 1,5-cyclooctadieneand butadienes; phosphorus ligands such as trimethylphosphine; and thelike are given.

The reducing agent mentioned above is desirably a strong reducing agentthat can reduce a metal in an iron, cobalt, or nickel salt up tozero-valence; for example, is preferably a reducing agent having anoxidation-reduction potential, with ferrocene as a standard, of lessthan or equal to −2.0 V in Non-Patent Document, Chem. Rev. 1996, 96,887-910, and is particularly preferably a reducing agent having anoxidation-reduction potential of less than or equal to −2.3 V.

Specific examples include alkali metals such as sodium and potassium;alkali metal alloys such as sodium-potassium and sodium amalgam; alkalimetal naphthalenide such as potassium naphthalenide; and the like, butare not limited to these.

Each of these alkali metals and alkali metal alloys may be one supportedby a solid substance; examples include sodium, potassium,sodium-potassium alloy, or the like supported by silica, alumina,graphite, titanium oxide, zeolite, zinc oxide, cerium oxide, orpolystyrene; among these, potassium-carrying graphite (hereinafter,abbreviated as KC₈) is preferable from the viewpoint of reactivity, andsodium-carrying silica (Stage 1 or 2) is preferable in terms of low riskof ignitability etc. from the viewpoint of safety.

An alkali metal supported by any of these solid substances may beobtained as, for example, one synthesized by a conventionally knownmethod such as a method described in JP 5048503B2, or may be obtained asa commercially available product, examples of which include KC₈(manufactured by Strem Chemicals, Inc.), Na silica gel (manufactured byAldrich Corporation, Stage I), Na silica gel (manufactured by AldrichCorporation, Stage II), NaK₂ silica gel (manufactured by AldrichCorporation, Stage I), and the like.

The ate-type iron-, cobalt-, or nickel-isocyanide complex mentionedabove is generally known as an ionic complex in which an iron-, cobalt-,or nickel-isocyanide complex is further reduced, and Na[Co(2,6-dimesitylisocyanide)₄] described in Non-Patent Document 51 and the like areknown.

Ferrocenium triflate or the like is given as an oxidizing agent in thecase where the synthesis is made by using an ate-type iron-, cobalt-, ornickel-isocyanide complex.

The isocyanide complex represented by formula (1) of the presentinvention is not particularly limited, and examples include thefollowing.

Specific examples of iron-isocyanide complexes include Fe(CNMe)₅,Fe(CNEt)₅, Fe(CN^(n)Pr)₅, Fe(CN^(i)Pr)₅, Fe(CN^(n)Bu)₅, Fe(CN^(t)Bu)₅,Fe(CNCy)₅, Fe(CNAd)₅, Fe(CNCF₃)₅, Fe(CNPh)₅, Fe(CNXylyl)₅, Fe(CNMes)₅,Fe(N₂)[CN-(2,6-bismesitylphenyl)]4, Fe[CN-(2-methyl-6-chlorophenyl)]₅,Fe[CN-(3,5-dimethoxyphenyl)]₅, Fe₂(CNEt)₉, and the like.

Specific examples of cobalt-isocyanide complexes include Co₂(CN^(t)Bu)₈,Co₂(CNCy)₈, Co₂(CNAd)₈, Co₂(CNPh)₈, Co₂(CNXylyl)₈, Co₂(CNMes)₈,Co₂[CN-(2-methyl-6-chlorophenyl)]₈, Co₂[CN-(3,5-dimethoxyphenyl)]₈,Co[CN-(2,6-bismesitylphenyl)]₄, and the like.

Specific examples of nickel-isocyanide complexes include Ni(CNMe)₄,Ni(CNEt)₄, Ni(CN^(t)Bu)₄, Ni₂(CN^(t)Bu)₄, Ni₃(CN^(t)Bu)₆, Ni(CNCy)₄,Ni(CNPh)₄, Ni(CNMes)₄, Ni(CNXylyl)₄, Ni[CN-(4-MeOC₆H₄)]₄,Ni[CN-(4-NO₂C₆H₄)]₄, Ni(CNC₆F₅)₄, Ni₄(CN^(t)Bu)₆, Ni₄(CN^(t)Bu)₇,Ni₄(CNMe)(CN^(t)Bu)₆, Ni₄(CNCy)₇, Ni₈(CN^(i)Pr)₁₂, and the like.

In the above, ^(n)Pr represents a n-propyl group, ^(i)Pr an isopropylgroup, ^(n)Bu a n-butyl group, ^(t)Bu a t-butyl group, Cy a cyclohexylylgroup, Ad an adamantyl group, Ph a phenyl group, Mes a mesityl group,and Xylyl a 2,6-dimethylphenyl group.

When performing reaction using the isocyanide complex of the presentinvention as a catalyst, the amount of the catalyst used is notparticularly limited; however, in view of obtaining the desired productwith good yield by progressing reaction under mild conditions ofapproximately 20 to 100° C., it is preferable that more than or equal to0.001 mol % of the isocyanide complex be used relative to 1 mol of acompound that is a substrate, it is more preferable that more than orequal to 0.01 mol % be used, and it is even more preferable that morethan or equal to 0.05 mol % be used. On the other hand, the upper limitof the amount of the isocyanide complex used is not particularly set,but is approximately 10 mol % relative to 1 mol of the substrate and ispreferably 5 mol %, from the economic point of view.

In the reaction using the catalyst of the present invention, a knowntwo-electron donating ligand may be used in combination to the extentthat the activity etc. of the catalyst are not impaired. Thetwo-electron donating ligand is not particularly limited, but ispreferably a ligand other than a carbonyl group, such as an ammoniamolecule, an ether compound, an amine compound, a phosphine compound, aphosphite compound, or a sulfide compound.

The isocyanide compound may be further added to the extent that theactivity etc. thereof are not impaired, and the addition amount in thiscase is preferably approximately 0.1 to 5 molar equivalents relative tothe catalyst of the present invention.

The conditions of reaction using the catalyst of the present inventionare not particularly limited; usually, the reaction temperature isapproximately 10 to 100° C., and preferably 20 to 80° C., and the periodof reaction is approximately 1 to 48 hours.

The reaction may be performed without a solvent, or may use an organicsolvent as necessary.

In the case where an organic solvent is used, examples of the kindinclude aliphatic hydrocarbons such as pentane, hexane, heptane, octane,and cyclohexane; ethers such as diethyl ether, diisopropyl ether,dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylenes,and mesitylene; and the like.

In the case where an organic solvent is used, the concentration of thecatalyst is preferably 0.01 to 10 M and more preferably 0.1 to 5 M asmolar concentration (M), in view of catalytic activity and economicalefficiency.

The catalyst of the present invention may be used as a catalyst forhydrosilylation reaction or hydrogenation reaction on an aliphaticunsaturated bond or hydrosilane reduction reaction on a carbon-oxygenunsaturated bond or a carbon-nitrogen unsaturated bond.

In the reaction using the catalyst of the present invention, all thecomponents may be collectively added, or components may be added inunits of several components.

By using the catalyst of the present invention for hydrosilylationreaction, a product of hydrosilylation reaction between an aliphaticunsaturated bond-containing compound and a Si—H bond-containing compoundis obtained.

As the use ratio between the aliphatic unsaturated bond-containingcompound and the Si—H bond-containing compound in hydrosilylationreaction, the molar ratio of aliphatic unsaturated bonds/Si—H bonds is1/10 to 10/1, preferably 1/5 to 5/1, and more preferably 1/3 to 3/1.

Specific examples of the aliphatic unsaturated bond-containing compoundinclude the following.

(1) Carbon-Carbon Unsaturated Bond-Containing Hydrocarbon Compounds

Alkenes such as ethylene, propylene, butylene, isobutylene, hexenes,octenes, decenes, dodecenes, n-hexadecene, isohexadecene, n-octadecene,isooctadecene, norbornene, and trifluoropropene; alkynes such as ethyne,propyne, butynes, pentynes, hexynes, octynes, decynes, dodecynes,hexadecynes, and octadecynes; and aromatic group-containing alkenes suchas styrene, 2-methylstyrene, 4-chlorostyrene, 4-methoxystyrene,α-methylstyrene, 4-methyl-α-methylstyrene, and allylbenzene.

(2) Allyl Ether Compounds

Allyl glycidyl ether, allyl glycol, allyl benzyl ether, diethyleneglycol monoallyl ether, diethylene glycol allyl methyl ether,polyoxyethylene monoallyl ether, polyoxypropylene monoallyl ether,poly(oxyethylene-oxypropylene) monoallyl ether, polyoxyethylene diallylether, polyoxypropylene diallyl ether, poly(oxyethylene-oxypropylene)diallyl ether, and the like.

(3) Nitrogen-Containing Alkene Compounds

Allylamine, N,N-dimethylallylamine, N,N-diethylallylamine,N,N-di(n-propyl)allylamine, N,N-diisopropylallylamine,N,N-di(n-butyl)allylamine, N,N-diisobutylallylamine,N-t-butylallylamine, N-allylcyclohexylamine, N-allylmorpholine,N,N-diallylamine, triallylamine, N-allylaniline, N-vinyl carbazole,N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone,N-vinylphthalimide, and the like.

(4) Carbon-Carbon Unsaturated Bond-Containing Silane Compounds

Trimethylvinylsilane, triethylvinylsilane, trimethoxyvinylsilane,triethoxyvinylsilane, dimethoxymethylvinylsilane,diethoxymethylvinylsilane, methoxydimethylvinylsilane,ethoxydimethylvinylsilane, trimethoxyallylsilane, triethoxyallylsilane,triisopropoxyvinylsilane, phenyldimethoxyvinylsilane,phenyldiethoxyvinylsilane, diphenylmethoxyvinylsilane,diphenylethoxyvinylsilane, triphenylvinylsilane, triphenylvinylsilane,and the like.

(5) Carbon-Carbon Unsaturated Bond-Containing Siloxane Compounds

Pentamethylvinyldisiloxane, tetramethyldivinyldisiloxane,heptamethylvinyltrisiloxane, dimethyldiphenyldivinyldisiloxane,dimethylvinylsiloxy group-end-capped dimethylpolysiloxane, and adimethylvinylsiloxy group-end-capped (dimethylsiloxane-diphenylsiloxane)copolymer. A trimethylsiloxy group-end-capped(dimethylsiloxane-methylvinylsiloxane) copolymer, a trimethylsiloxygroup-end-capped (dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane)copolymer, a dimethylvinylsiloxy group-end-capped(dimethylsiloxane-methylvinylsiloxane) copolymer, a dimethylvinylsiloxygroup-end-capped (dimethylsiloxane-methylvinylsiloxane-diphenylsiloxane)copolymer, a hydroxy group-end-capped(dimethylsiloxane-methylvinylsiloxane) copolymer,α-vinyldimethylpolysiloxane, and the like.

In the aliphatic unsaturated bond-containing compound mentioned above,an unsaturated bond may exist at a molecular end or may exist in theinterior, or a plurality of unsaturated bonds may exist in the moleculelike in hexadienes and octadienes.

Also an alkene compound having a sulfide group like those shown belowmay be used as the aliphatic unsaturated bond-containing compound. Inthis case, unlike a silicon compound in which silicon is bonded tocarbon at an end of an alkene, which is known in the case where aplatinum catalyst is used, isomerization reaction of an alkene occurs,and a silicon compound in which silicon is bonded onto carbon adjacentto the sulfur element is obtained selectively.

(6) Alkene Compounds Having Sulfide Group

Methyl vinyl sulfide, ethyl vinyl sulfide, n-propyl vinyl sulfide,isopropyl vinyl sulfide, n-butyl vinyl sulfide, phenyl vinyl sulfide,benzyl vinyl sulfide, methyl allyl sulfide, ethyl allyl sulfide,n-propyl allyl sulfide, isopropyl allyl sulfide, n-butyl allyl sulfide,isobutyl allyl sulfide, phenyl allyl sulfide, benzyl allyl sulfide,allyl (n-propyl) disulfide, diallyl sulfide, diallyl disulfide, and thelike.

Examples of the Si—H bond-containing compound include the followingsilanes and siloxanes.

(1) Silanes

Trimethoxysilane, triethoxysilane, triisopropoxysilane,dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane,diethoxyphenylsilane, methoxydimethylsilane, ethoxydimethyl silane,triphenyl silane, diphenyldisilane, phenyltrisilane, diphenylmethylsilane, phenyldimethylsilane, diphenylmethoxysilane,diphenylethoxysilane, and the like.

(2) Siloxanes

Pentamethyldisiloxane, tetramethyldisiloxane, heptamethyltrisiloxane,octamethyltetrasiloxane, dimethyl hydrogen siloxy group-end-cappeddimethylpolysiloxane, dimethyl hydrogen siloxy group-end-capped methylhydrogen polysiloxane, trimethylsiloxy group-end-capped methyl hydrogenpolysiloxane, a dimethyl hydrogen siloxy group-end-capped(dimethylsiloxane-diphenylsiloxane) copolymer, a trimethylsiloxygroup-end-capped (dimethyl siloxane-methylhydrosiloxane) copolymer, atrimethylsiloxy group-end-capped (dimethylsiloxane-diphenylsiloxane-methylhydrogensiloxane) copolymer, a dimethylhydrogen siloxy group-end-capped (dimethylsiloxane-methylhydrogensiloxane) copolymer, a dimethyl hydrogen siloxygroup-end-capped(dimethylsiloxane-methylhydrogensiloxane-diphenylsiloxane) copolymer, ahydroxy group-end-capped (dimethyl siloxane-methylhydrogensiloxane)copolymer, dimethyl hydrogen siloxy group-one-end-cappeddimethylpolysiloxane, and the like.

Further, by reacting together an aliphatic unsaturated bond-containingcompound and a hydrogen molecule in the presence of the catalyst of thepresent invention, a corresponding compound having a saturated bond isobtained.

Specific examples of the aliphatic unsaturated bond-containing compoundinclude compounds similar to those given as examples in hydrosilylationreaction mentioned above.

As a means for introducing a hydrogen molecule into a reaction system inhydrogenation reaction, introduction may be made while gas containinghydrogen molecules is caused to flow or bubble in a reactor, or reactionmay be performed in a pressure resistant vessel in which gas containinghydrogen molecules is enclosed. The pressure at this time is notparticularly limited, but is preferably 0.1 to 3 MPa and more preferably0.1 to 2 MPa from the viewpoint of safety.

Further, a product of hydrosilane reduction reaction between a compoundhaving a carbon-oxygen unsaturated bond or a carbon-nitrogen unsaturatedbond and a Si—H bond-containing compound is obtained in the presence ofthe catalyst of the present invention.

In this case, the use ratio between the compound having a carbon-oxygenunsaturated bond or a carbon-nitrogen unsaturated bond and the Si—Hbond-containing compound is not particularly limited; however, as themolar ratio, (carbon-oxygen unsaturated bonds or carbon-nitrogenunsaturated bonds)/(Si—H bonds) is preferably 1/10 to 1/1, morepreferably 1/5 to 1/1, and still more preferably 1/3 to 1/1.

As the Si—H bond-containing compound used in hydrosilane reductionreaction of a compound having a carbon-oxygen unsaturated bond or acarbon-nitrogen unsaturated bond of the present invention, compoundssimilar to those shown as examples in hydrosilylation reaction mentionedabove are given; in view of reactivity and economical efficiency, amongthem, aryl group-containing silanes such as phenylsilane,diphenylsilane, and dimethylphenylsilane; a siloxane containing Si—Hgroups adjacent via an oxygen atom, such as1,1,3,3-tetramethyldisiloxane, trimethylsiloxy group-end-capped methylhydrogen polysiloxane, and dimethyl hydrogen siloxy group-end-cappedmethyl hydrogen polysiloxane, are preferable, and1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3-pentamethyldisiloxane,1,1,1,3,5,5,5-heptamethyltrisiloxane, trimethylsiloxy group-end-cappedmethyl hydrogen polysiloxane, and dimethyl hydrogen siloxygroup-end-capped methyl hydrogen polysiloxane are more preferable.

As the compound having a carbon-oxygen unsaturated bond or acarbon-nitrogen unsaturated bond that can be used for hydrosilanereduction reaction, a compound having an aldehyde, ketone, amide, ornitrile group, and the like are given; by reacting any of thesecompounds with a silane or a siloxane containing a Si—H group in thepresence of the catalyst of the present invention and performing knownpost-treatment, the compound can be turned into a respectivecorresponding amine or alcohol compound.

Specific examples of the compound having a carbon-oxygen unsaturatedbond or a carbon-nitrogen unsaturated bond include acetophenone,N,N-dimethylbenzamide, acetonitrile, and the like.

EXAMPLES

Synthesis Examples, Examples and Comparative Examples are given below byway of illustration and not by way of limitation.

All solvents were deoxygenated and dehydrated by well-known methodsbefore they were used in the preparation of catalysts.

The catalysts obtained were stored in a nitrogen gas atmosphere at 25°C. until they were used in reaction.

Hydrosilylation reaction and solvent purification were always carriedout in an inert gas atmosphere. The solvents and other ingredients werepurified, dried and deoxygenated by well-known methods before they wereused in various reactions.

The measurement of ¹H-NMR was performed using JNM-ECA600 and JNM-LA400manufactured by JEOL Ltd, and IR measurement was performed usingFT/IR-550 manufactured by JASCO Corporation.

In the chemical structure formulae shown below, hydrogen atoms areomitted in accordance with common expression.

[Synthesis Example 1] Synthesis of Cobalt Isocyanide ComplexCo₂(CN^(t)Bu)₈

Cobalt iodide (0.31 g, 1.0 mmol), tetrahydrofuran (hereinafter,abbreviated as THF) (15 mL), t-butyl isocyanide (0.33 g, 4.0 mmol), andKC₈ (manufactured by Strem Chemicals, Inc., 0.27 g, 2.0 mmol) were addedin this order to a reactor, and stirring was performed at 25° C. for 12hours. After that, the reaction solution was subjected to celitefiltration, and the solvent of the filtrate was distilled under reducedpressure. The resulting dried substance was dissolved in pentane(approximately 40 mL), and the insoluble matter was removed by celitefiltration. The filtrate was cooled to −35° C. to performrecrystallization; thus, Co₂(CN^(t)Bu)₈ was obtained (0.24 g, 61%).

¹H-NMR (600 MHz, C₆D₆) δ: 1.44 (s, 72H).

IR (ATR): v=1666 (CN (bridge)), 2093, 1977, 1942 (CN (terminal)) cm⁻¹

Anal. Calcd. for C₄₀H₇₂N₈Co₂:

C: 61.36; H: 9.27; N: 14.31; Found: C: 61.06; H: 9.52; N: 14.05.

[Synthesis Example 2] Synthesis of Cobalt Isocyanide Complex Co₂(CNAd)₈

0.31 g (1.0 mmol) of cobalt iodide, 0.65 g (4.0 mmol) of1-isocyanoadamantane (hereinafter, abbreviated as CNAd), THF (15 mL),and KC₈ (0.27 g, 2.0 mmol) were added in this order to a reactor, andstirring was performed at 25° C. for 12 hours. After that, the reactionsolution was subjected to celite filtration, and the solvent of thefiltrate was distilled under reduced pressure. The resulting driedsubstance was dissolved in toluene (approximately 20 ml), and celitefiltration was performed again. The solvent of the filtrate wasdistilled under reduced pressure, and then the dried substance waswashed with a small amount of benzene (approximately 3 ml); thus,Co₂(CNAd)₈ was obtained (0.33 g, 47%).

¹H-NMR (396 MHz, C₆D₆) δ:

2.32 (s, 48H), 2.06 (s, 24H), 1.71 (d, J=10.3, 24H), 1.58 (d, J=10.3,24H).

IR (ATR): v=1647 (CN (bridge)), 2101, 2000, 1954 (CN (terminal)) cm⁻¹

Anal. Calcd. for C₈₈H₁₂₀N₈Co₂:

C: 75.08; H: 8.59; N: 7.96; Found: C: 75.16; H: 8.62; N: 7.46.

[Synthesis Example 3] Synthesis of Cobalt Isocyanide Complex Co₂(CNMes)₈

Cobalt iodide (13 mg, 0.10 mmol), mesityl isocyanide (58 mg, 0.40 mmol),THF (3 mL), and KC₈ (27 mg, 0.20 mmol) were added in this order to areactor, and stirring was performed at 25° C. for 12 hours. After that,the reaction solution was subjected to celite filtration, and thesolvent of the filtrate was distilled under reduced pressure. Theresulting dried substance was dissolved in toluene (approximately 3 mL),and the insoluble matter was removed by celite filtration. Pentane(approximately 3 mL) was slowly added from above the filtrate to performrecrystallization; thus, a cobalt isocyanide complex of Co₂(CNMes)₈ wasobtained (42 mg, 66%).

¹H-NMR (396 MHz, C₆D₆) δ:

6.60 (s, 12H), 6.58 (s, 4H), 2.46 (s, 36H), 2.42 (s, 12H), 2.05 (s,18H), 2.03 (s, 6H).

IR (ATR): v=1669 (CN (bridge)), 2063, 2026, 1954 (CN (terminal)) cm⁻¹

Anal. Calcd. for C₈₀H₈₈N₈Co₂:

C: 75.10; H: 6.93; N: 8.60; Found: C: 75.21; H: 6.90; N: 8.60.

[Synthesis Example 4] Synthesis of Iron Isocyanide Complex Fe(CN^(t)Bu)₅

Iron bromide (22 mg, 0.10 mmol), THF (3 mL), t-butyl isocyanide (42 mg,0.50 mmol), and KC₈ (27 mg, 0.20 mmol) were added in this order to areactor, and stirring was performed at 25° C. for 12 hours. After that,the reaction solution was subjected to celite filtration, and thesolvent of the filtrate was distilled under reduced pressure. Theresulting dried substance was dissolved in pentane (approximately 4 mL),and the insoluble matter was removed by celite filtration. The filtratewas cooled to −35° C. to perform recrystallization; thus, Fe(CN^(t)Bu)₅was obtained (30 mg, 63%).

¹H-NMR (600 MHz, C₆D₆) δ: 1.29 (s, 45H).

IR (ATR): v=2119, 2000, 1943, 1826 (CN) cm⁻¹

[Synthesis Example 5] Synthesis of Iron Isocyanide Complex Fe(CNAd)₅Using Iron Bromide and KC₈

Iron bromide (216 mg, 1.0 mmol), THF (20 mL), adamantyl isocyanide (806mg, 5.0 mmol), and KC₈ (manufactured by Strem Chemicals, Inc., 270 mg,2.0 mmol) were added in this order to a reactor, and stirring wasperformed at 25° C. for 12 hours. After that, the reaction solution wassubjected to celite filtration, and the solvent of the filtrate wasdistilled under reduced pressure. The resulting dried substance wasdissolved in benzene (approximately 5 mL), and the insoluble matter wasremoved by celite filtration. Pentane was added to the filtrate, andthen cooling was performed to −35° C. to perform recrystallization;thus, Fe(CNAd)₅ was obtained (601 mg, yield: 70%).

¹H-NMR (396 MHz, C₆D₆) δ:

2.15 (s, 30H), 1.88 (s, 15H), 1.50 (d, J=11.5, 15H), 1.42 (d, J=11.5,15H).

IR (ATR): v=2106 (CN) cm⁻¹

[Synthesis Example 6] Synthesis of Nickel Isocyanide Complex Ni (CNtBu)₄Using Nickel Bromide (Dimethoxyethane Adduct) and KC₈

Nickel bromide (a dimethoxyethane adduct) (31 mg, 0.1 mmol), THF (3 mL),t-butyl isocyanide (0.33 g, 0.4 mmol), and KC₈ (270 mg, 2.0 mmol) wereadded in this order to a reactor, and stirring was performed at roomtemperature for 30 minutes. After that, the reaction solution wassubjected to celite filtration, and the solvent of the filtrate wasdistilled under reduced pressure. The resulting dried substance wasdissolved in benzene (approximately 5 mL), and the insoluble matter wasremoved by celite filtration. Ether was added to the filtrate, and thencooling was performed to −35° C. to perform recrystallization; thus,Ni(CN^(t)Bu)₄ was obtained (21 mg, yield: 54%).

¹H-NMR (396 MHz, C₆D₆) δ: 1.09 (s, 36H).

IR (ATR): v=2002 (CN) cm⁻¹

[1] Hydrosilylation Reaction Using Alkene as Substrate [Example 1]Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxane ofα-Methylstyrene Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),α-methylstyrene (129 μL, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane(254 μL, 1.3 mmol) were added to a reactor, and stirring was performedat 25° C. for 24 hours. After the reaction ended, ¹H-NMR spectrum wasmeasured to determine the structure and the yield of the product. Amultiplet at 0.94 ppm, which is a signal of protons on carbon adjacentto silicon in the desired product, was observed, and the yield wasfound. The results are shown in Table 1.

¹H-NMR (396 MHz, CDCl₃) δ:

7.27 (t, J=6.8, 2H), 7.21 (d, J=6.8, 2H), 7.15 (t, J=6.8, 1H), 2.91(sext, J=6.8, 1H), 1.28 (d, J=6.8, 3H), 0.90-0.98 (m, 2H), 0.05 (s, 9H),−0.05 (s, 3H), −0.07 (s, 3H).

Examples 2 and 3

Reaction was performed in a similar manner to Example 1 except that, inplace of Co₂(CN^(t)Bu)₈, the cobalt-isocyanide complexes written inTable 1 (each 0.005 mmol) were used as catalysts. The results are shownin Table 1 below.

Comparative Example 1 Hydrosilylation Reaction by1,1,1,3,3-Pentamethyldisiloxane of α-Methylstyrene Using, as Catalyst,Composition Consisting of Cobalt Pivalate, CNAd, andDiethoxymethylsilane

3 mg (0.01 mmol) of cobalt pivalate, 5 mg (0.03 mmol) of CNAd, and 100μL of THF were added to a reactor, and were dissolved. 5.3 mg (0.04mmol) of diethoxymethylsilane was added to the reactor, and stirring wasperformed at 25° C. for 1 hour. After that, α-methylstyrene (129 μL, 1.0mmol) and 1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) were added,and stirring was performed at 25° C. for 24 hours. After the reactionended, ¹H-NMR spectrum was measured to determine the structure and theyield of the product. A multiplet at 0.94 ppm, which is a signal ofprotons on carbon adjacent to silicon in the desired product, wasobserved, and the yield was found. The results are shown in Table 1.

TABLE 1 Conver- sion Yield Catalyst (%) (%) Example 1Co₂(CN^(t)Bu)₈ >99 >99 Example 2 Co₂(CNAd)₈ >99 >99 Example 3Co₂(CNMes)₈ >99 >99 Comparative Example 1 cobalt pivalate/CNAd/ 10 10diethoxymethylsilane

[Example 4] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof α-Methylstyrene Using Co₂(CNAd)₈ as Catalyst

Co₂(CNAd)₈ obtained in Synthesis Example 2 (6.4 mg, 0.0005 mmol),α-methylstyrene (1.29 mL, 10 mmol), and 1,1,1,3,3-pentamethyldisiloxane(2.54 mL, 13 mmol) were added to a reactor, and stirring was performedat 80° C. for 24 hours. After the reaction ended, ¹H-NMR spectrum wasmeasured to determine the structure and the yield of the product. Amultiplet at 0.94 ppm, which is a signal of protons on carbon adjacentto silicon in the desired product, was observed, and the yield wasfound. The results are shown in Table 2.

Comparative Example 2 Hydrosilylation Reaction by1,1,1,3,3-Pentamethyldisiloxane of α-Methylstyrene Using Co₂(CO)₈ asCatalyst

Co₂(CO)₈ (1.7 mg, 0.0005 mmol), α-methylstyrene (1.29 mL, 10 mmol), and1,1,1,3,3-pentamethyldisiloxane (2.54 mL, 13 mmol) were added to areactor, and stirring was performed at 80° C. for 24 hours. After thereaction ended, ¹H-NMR spectrum was measured to determine the structureand the yield of the product. A multiplet at 0.94 ppm, which is a signalof protons on carbon adjacent to silicon in the desired product, wasobserved, and the yield was found. The results are shown in Table 2.

TABLE 2 Conver- sion Yield Catalyst (%) (%) Example 4 Co₂(CNAd)₈ >99 >99Comparative Example 2 Co₂(CO)₈ 88 88

[Example 5] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof Styrene Using Fe(CN^(t)Bu)₅ as Catalyst

Fe(CN^(t)Bu)₅ obtained in Synthesis Example 4 (4.7 mg, 0.01 mmol),styrene (114 μL, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 μL,1.3 mmol) were added to a reactor, and stirring was performed at 25° C.for 24 hours. After the reaction ended, ¹H-NMR spectrum was measured todetermine the structure and the yield of the product. A multiplet at0.90 ppm, which is a signal of protons on carbon adjacent to silicon inthe desired product, was observed, and the yield was found. The resultsare shown in Table 3.

¹H-NMR (396 MHz, CDCl₃) δ:

7.24-7.29 (m, 2H), 7.13-7.22 (m, 3H), 2.61-2.68 (m, 2H), 0.86-0.92 (m,2H), 0.08 (s, 9H), 0.07 (s, 6H).

[Example 6] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof 1-Octene Using Co₂(CNMes)₈ as Catalyst

Co₂(CNMes)₈ obtained in Synthesis Example 3 (6.4 mg, 0.005 mmol),1-octene (157 μL, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254μL, 1.3 mmol) were added to a reactor, and stirring was performed at 25°C. for 24 hours. After the reaction ended, ¹H-NMR spectrum was measuredto determine the structure and the yield of the product. A multiplet at0.50 ppm, which is a signal of protons on carbon adjacent to silicon inthe desired product, was observed, and the yield was found. The resultsare shown in Table 3.

¹H-NMR (396 MHz, CDCl₃) δ:

1.21-1.37 (m, 12H), 0.88 (t, J=6.8, 3H), 0.50 (m, 2H), 0.06 (s, 9H),0.03 (s, 6H).

[Example 7] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof Styrene Using Co₂(CNMes)₈ as Catalyst

Co₂(CNMes)₈ obtained in Synthesis Example 3 (6.4 mg, 0.005 mmol),styrene (114 μL, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 μL,1.3 mmol) were added to a reactor, and stirring was performed at 25° C.for 24 hours. After the reaction ended, ¹H-NMR spectrum was measured todetermine the structure and the yield of the product. A multiplet at0.90 ppm, which is a signal of protons on carbon adjacent to silicon inthe desired product, was observed, and the yield was found. The resultsare shown in Table 3.

¹H-NMR (396 MHz, CDCl₃) δ:

7.24-7.29 (m, 2H), 7.13-7.22 (m, 3H), 2.61-2.68 (m, 2H), 0.86-0.92 (m,2H), 0.08 (s, 9H), 0.07 (s, 6H).

[Example 8] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof Allyl Glycidyl Ether Using Co₂(CNAd)₈ as Catalyst

Co₂(CNAd)₈ obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol), allylglycidyl ether (118 μL, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane(254 μL, 1.3 mmol) were added to a reactor, and stirring was performedat 25° C. for 24 hours. After the reaction ended, ¹H-NMR spectrum wasmeasured to determine the structure and the yield of the product. Amultiplet at 0.51 ppm, which is a signal of protons on carbon adjacentto silicon in the desired product, was observed, and the yield wasfound. The results are shown in Table 3.

¹H-NMR (396 MHz, CDCl₃) δ:

3.71 (dd, J=11.6, J=3.9, 1H) 3.37-3.51 (m, 3H), 3.26 (dt, J=2.9, J=6.3,1H), 2.62 (t, J=4.4, 1H), 2.62 (q, J=2.9, 1H), 1.59-1.65 (m, 2H),0.49-0.53 (m, 2H), 0.06 (s, 9H).

TABLE 3 Conver- sion Yield Alkene Catalyst (%) (%) Example 5 styreneFe(CN^(t)Bu)₅ >99 99 Example 6 1-octene Co₂(CNMes)₈ >99 24 Example 7styrene Co₂(CNMes)₈ 90 44 Example 8 allyl glycidyl ether Co₂(CNAd)₈ >9990

[Example 9] Hydrosilylation Reaction by1,1,1,3,5,5,5-Heptamethyltrisiloxane of α-Methylstyrene UsingCo₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),α-methylstyrene (129 μL, 1.0 mmol), and1,1,1,3,5,5,5-heptamethyltrisiloxane (351 μL, 1.3 mmol) were added to areactor, and stirring was performed at 80° C. for 24 hours. After thereaction ended, ¹H-NMR spectrum was measured to determine the structureand the yield of the product. A multiplet at 0.88 ppm, which is a signalof protons on carbon adjacent to silicon in the desired product, wasobserved, and the yield was found. The results are shown in Table 4.

¹H-NMR (396 MHz, CDCl₃) δ:

7.27 (t, J=6.8, 2H), 7.21 (d, J=6.8, 2H), 7.16 (t, J=6.8, 1H), 2.92(sext, J=6.8, 1H), 1.28 (d, J=6.8, 3H), 0.82-0.94 (m, 2H), 0.09 (s, 9H),0.07 (s, 9H), −0.12 (s, 3H).

[Example 10] Hydrosilylation Reaction by Triethoxysilane ofα-Methylstyrene Using Co₂(CNAd)₈ as Catalyst

Co₂(CNAd)₈ obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol),α-methylstyrene (129 μL, 1.0 mmol), and triethoxysilane (213 mg, 1.3mmol) were added to a reactor, and stirring was performed at 80° C. for24 hours. After the reaction ended, ¹H-NMR spectrum was measured todetermine the structure and the yield of the product. A sextet at 3.00ppm, which is a signal of protons on carbon adjacent to a phenyl groupin the desired product, was observed, and the yield was found. Theresults are shown in Table 4.

¹H-NMR (396 MHz, CDCl₃) δ:

7.27 (t, J=6.8, 2H), 7.21 (d, J=6.8, 2H), 7.15 (t, J=6.8, 1H), 3.73 (q,J=6.8, 6H), 2.96 (sext, J=6.8, 1H), 1.31 (d, J=6.8, 3H), 1.18 (m, J=6.8,9H), 1.03 (d, J=6.8, 2H).

[Example 11] Hydrosilylation Reaction by Diethoxy(Methyl)Silane ofα-Methylstyrene Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),α-methylstyrene (129 μL, 1.0 mmol), and diethoxy(methyl)silane (175 mg,1.3 mmol) were added to a reactor, and stirring was performed at 50° C.for 24 hours. After the reaction ended, ¹H-NMR spectrum was measured todetermine the structure and the yield of the product. A sextet at 2.96ppm, which is a signal of protons on carbon adjacent to a phenyl groupin the desired product, was observed, and the yield was found. Theresults are shown in Table 4.

¹H-NMR (396 MHz, CDCl₃) δ:

7.27 (t, J=6.8, 2H), 7.21 (d, J=6.8, 2H), 7.15 (t, J=6.8, 1H), 3.63-3.70(m, 4H), 3.00 (sext, J=6.8, 1H), 1.32 (d, J=6.8, 3H), 1.21 (t, J=6.8,3H), 1.15 (t, J=6.8, 3H), 1.03 (d, J=6.8, 2H), −0.08 (s, 3H).

TABLE 4 Conver- sion Yield Silane Catalyst (%) (%) Example 91,1,1,3,5,5,5- Co₂(CN^(t)Bu)₈ >99 >99 heptamethyltrisiloxane Example 10triethoxysilane Co₂(CNAd)₈ 84 45 Example 11 Diethoxy(methyl)silaneCo₂(CN^(t)Bu)₈ >99 92

[Example 12] Hydrosilylation Reaction by Polydimethylsiloxane Endblockedat Both Terminals by Dimethylhydrogensiloxy Groups of Allyl GlycidylEther Using Co₂(CNAd)₈ as Catalyst

Co₂(CNAd)₈ obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol), allylglycidyl ether (154 μL, 1.3 mmol), and polydimethylsiloxane endblockedat both terminals by dimethylhydrogensiloxy groups (degree ofpolymerization 18) (0.74 g, 0.50 mmol) were added to a reactor, andstirring was performed at 50° C. for 24 hours. After the reaction ended,¹H-NMR spectrum was measured to determine the structure and the yield ofthe product. A multiplet at 0.54 ppm, which is a signal of protons oncarbon adjacent to silicon in the desired product, was observed, and theyield was found (yield >99%).

¹H-NMR (396 MHz, CDCl₃) δ:

3.70 (m, 1H), 2.95-2.90 (m, 2H), 3.45 (m, 3H), 3.15 (m, 1H), 2.80 (m,1H), 2.61 (m, 1H), 1.62 (m, 2H), 0.54 (m, 2H), 0.08 (br), 0.05 (s),−0.08 (s).

[2] Hydrosilylation Reaction Using Sulfur-Containing Alkene as Substrate

[Example 13] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof Ethyl Vinyl Sulfide Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),ethyl vinyl sulfide (88 mg, 1.0 mmol), and1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) were added to areactor, and stirring was performed at 25° C. for 24 hours. After thereaction ended, isolation and purification were performed by silica gelchromatography, and 239 mg of the desired product was obtained. Yieldsare shown in Table 5.

¹H-NMR (400 MHz, CDCl₃) δ:

0.08 (s, 9H, —SiMe₃), 0.12 (s, 3H), 0.16 (s, 3H), 0.98 (t, J=7.32 Hz,3H), 1.50-1.65 (m, 3H), 1.68-1.71 (m, 1H), 1.75-1.81 (m, 1H), 2.49 (t,2H).

[Example 14] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof Phenyl Vinyl Sulfide Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (6.0 mg, 0.0075 mmol),phenyl vinyl sulfide (68 mg, 0.5 mmol), and1,1,1,3,3-pentamethyldisiloxane (223 mg, 1.5 mmol) were added to areactor, and stirring was performed at 25° C. for 24 hours. After thereaction ended, isolation and purification were performed by Kugelrohrdistillation, and 129 mg of the desired product was obtained. Yields areshown in Table 5.

¹H-NMR (400 MHz, CDCl₃)

δ: 0.11 (s, 9H), 0.18 (s, 3H), 0.20 (s, 3H), 1.31 (d, J=7.73 Hz, 3H),2.54 (q, J=7.09 Hz, 1H), 7.28 (dd, J=7.73, 9.67 Hz, 1H), 7.28 (d, J=7.73Hz, 2H), 7.35 (d, J=9.67 Hz, 2H).

[Example 15] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof Methyl Allyl Sulfide Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),methyl allyl sulfide (88 mg, 1.0 mmol), and1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) were added to areactor, and stirring was performed at 25° C. for 24 hours. After thereaction ended, isolation and purification were performed by silica gelchromatography, and 209 mg of the desired product was obtained. Yieldsare shown in Table 5.

¹H-NMR (400 MHz, CDCl₃) δ:

0.08 (s, 9H), 0.13 (s, 3H), 0.16 (s, 3H), 1.06 (t, J=7.14 Hz, 3H),1.57-1.62 (m, 2H), 1.75-1.81 (m, 1H), 2.09 (s, 3H).

[Example 16] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof n-Propyl Allyl Sulfide Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),n-propyl allyl sulfide (116 mg, 1.0 mmol), and1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) were added to areactor, and stirring was performed at 25° C. for 24 hours. After thereaction ended, isolation and purification were performed by silica gelchromatography, and 239 mg of the desired product was obtained. Yieldsare shown in Table 5.

¹H-NMR (400 MHz, CDCl₃) δ:

0.08 (s, 9H), 0.12 (s, 3H), 0.16 (s, 3H), 0.98 (t, J=7.32 Hz, 3H),1.50-1.65 (m, 3H), 1.68-1.71 (m, 1H), 1.75-1.81 (m, 1H), 2.49 (t, 2H).

[Example 17] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof Phenyl Allyl Sulfide Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (9.7 mg, 0.0125 mmol),phenyl allyl sulfide (75 mg, 0.5 mmol), and1,1,1,3,3-pentamethyldisiloxane (127 μL, 0.65 mmol) were added to areactor, and stirring was performed at 25° C. for 24 hours. After thereaction ended, isolation and purification were performed by Kugelrohrdistillation, and 142 mg of the desired product was obtained. Yields areshown in Table 5.

¹H-NMR (600 MHz, CDCl₃) δ:

0.10 (s, 9H), 0.19 (s, 3H), 0.19 (s, 3H), 1.31 (t, J=7.42 Hz, 3H), 1.67(dqd, J=6.04, 7.42, 13.74 Hz, 1H),

1.81 (dqd, 6.04, 7.42, 13.74 Hz, 1H), 7.14 (td, J=7.42, 2.75 Hz, 1H),7.25-7.26 (m, 2H), 7.35 (dd, J=8.24, 1.10 Hz, 2H).

[Example 18] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof Benzyl Allyl Sulfide Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),benzyl allyl sulfide (164 mg, 1.0 mmol), and1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) were added to areactor, and stirring was performed at 25° C. for 24 hours. After thereaction ended, isolation and purification were performed by Kugelrohrdistillation, and 245 mg of the desired product was obtained. Yields areshown in Table 5.

¹H-NMR (400 MHz, CDCl₃) δ:

0.05 (s, 9H), 0.06 (s, 3H), 1.01 (t, J=7.32 Hz, 3H), 1.53-1.62 (m, 1H),1.63-1.67 (m, 1H), 1.69-1.80 (m, 1H), 3.66-3.75 (m, 2H), 7.22-7.30 (m,5H).

Comparative Example 3 Hydrosilylation Reaction by1,1,1,3,3-Pentamethyldisiloxane of Methyl Allyl Sulfide Using Co₂(CO)₈as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),methyl allyl sulfide (88 mg, 1.0 mmol), and1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) were added to areactor, and stirring was performed at 25° C. for 24 hours. After thereaction ended, ¹H-NMR spectrum was measured; as a result, only thesource material was observed, and a product was not seen (a yield of0%).

TABLE 5 Isolated Conversion Yield yield Sulfur-containing alkene Product(%) (%) (%) Example 13

>99 >99 90 Example 14

>99 >99 90 Example 15

>99 >99 89 Example 16

>99 >99 90 Example 17

>99 97 95 Example 18

>99 >99 92

[3] Hydrosilylation Reaction Using Nitrogen-Containing Alkene asSubstrate

[Example 19] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof N-Allylaniline Using Co₂(CNAd)₈ as Catalyst

Co₂(CNAd)₈ obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol),N-allylaniline (133 mg, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane(254 μL, 1.3 mmol) were added to a reactor, and stirring was performedat 25° C. for 24 hours. After the reaction ended, ¹H-NMR spectrum wasmeasured to determine the structure and the yield of the product. Amultiplet at 0.59 ppm, which is a signal of protons on carbon adjacentto silicon in the desired product, was observed, and the yield wasfound. The results are shown in Table 6.

¹H-NMR (400 MHz, CDCl₃) δ:

0.07 (s, 15H), 0.59 (m, 2H), 1.63 (m, 2H), 3.10 (q, J=5.8, 2H), 3.66(br, 1H), 6.60 (d, J=7.7, 2H), 6.68 (t, J=7.7, 1H), 7.17 (t, J=7.2, 2H).

[Example 20] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof N,N-Diethylallylamine Using Co₂(CNAd)₈ as Catalyst

Co₂(CNAd)₈ obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol),N,N-diethylallylamine (113 mg, 1.0 mmol), and1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) were added to areactor, and stirring was performed at 50° C. for 24 hours. After thereaction ended, ¹H-NMR spectrum was measured to determine the structureand the yield of the product. A multiplet at 0.46 ppm, which is a signalof protons on carbon adjacent to silicon in the desired product, wasobserved, and the yield was found. The results are shown in Table 6.

¹H-NMR (400 MHz, CDCl₃) δ:

0.03 (s, 9H), 0.04 (s, 3H), 0.05 (s, 3H), 0.46 (m, 2H), 1.02 (t, J=7.4,6H), 1.47 (m, 2H), 2.40 (t, J=8.0, 2H), 2.52 (q, J=7.4, 4H).

[Example 21] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof 9-Vinylcarbazole Using Co₂(CNMes)₈ as Catalyst

Co₂(CNMes)₈ obtained in Synthesis Example 3 (6.4 mg, 0.005 mmol),N-methyl pyrrolidone (100 μL) as a solvent, 9-vinylcarbazole (193 mg,1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) wereadded to a reactor, and stirring was performed at 25° C. for 24 hours.After the reaction ended, ¹H-NMR spectrum was measured to determine thestructure and the yield of the product. A multiplet at 1.16 ppm, whichis a signal of protons on carbon adjacent to silicon in the desiredproduct, was observed, and the yield was found. The results are shown inTable 6.

¹H-NMR (400 MHz, CDCl₃) δ:

0.15 (s, 6H), 0.17 (s, 9H), 1.16 (m, 2H), 4.38 (m, 2H), 7.23 (t, J=7.7Hz, 2H), 7.39 (d, J=7.7 Hz, 2H), 7.47 (t, J=7.7 Hz, 2H), 8.11 (d, J=7.7Hz, 2H).

[Example 22] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof N-Vinylphthalimide Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol), DME(100 μL) as a solvent, N-vinylphthalimide (173 mg, 1.0 mmol), and1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) were added to areactor, and stirring was performed at 50° C. for 24 hours. After thereaction ended, ¹H-NMR spectrum was measured to determine the structureand the yield of the product. A multiplet at 1.03 ppm, which is a signalof protons on carbon adjacent to silicon in the desired product, wasobserved, and the yield was found. The results are shown in Table 6.

¹H-NMR (400 MHz, CDCl₃) δ:

0.07 (s, 9H), 0.14 (s, 6H), 1.03 (m, 2H), 3.75 (m, 2H), 7.69-7.80 (m,4H).

[Example 23] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof N-Vinyl-2-Pyrrolidone Using Co₂(CNAd)₈ as Catalyst

Co₂(CNAd)₈ obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol),N-vinyl-2-pyrrolidone (111 mg, 1.0 mmol), and1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) were added to areactor, and stirring was performed at 50° C. for 24 hours. After thereaction ended, ¹H-NMR spectrum was measured to determine the structureand the yield of the product. A multiplet at 0.81 ppm, which is a signalof protons on carbon adjacent to silicon in the desired product, wasobserved, and the yield was found. The results are shown in Table 6.

¹H-NMR (400 MHz, CDCl₃) δ:

0.08 (s, 9H), 0.10 (s, 6H), 0.82 (m, 2H), 2.00 (quint, J=7.2, 2H), 2.36(t, J=7.7, 2H), 3.36 (m, 4H).

Comparative Example 4 Hydrosilylation Reaction by1,1,1,3,3-Pentamethyldisiloxane of N-Vinyl-2-Pyrrolidone Using Co₂(CO)₈as Catalyst

Co₂(CO)₈ (1.7 mg, 0.005 mmol), N-vinyl-2-pyrrolidone (111 mg, 1.0 mmol),and 1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) were added to areactor, and stirring was performed at 50° C. for 24 hours. After thereaction ended, ¹H-NMR spectrum was measured to determine the structureand the yield of the product. A multiplet at 0.81 ppm, which is a signalof protons on carbon adjacent to silicon in the desired product, wasobserved, and the yield was found. The results are shown in Table 6.

TABLE 6 Nitrogen-containing Conversion Yield alkene Product Catalyst (%)(%) Example 19

Co₂(CNAd)₈ >99 41 Example 20

Co₂(CNAd)₈ >99 73 Example 21

Co₂(CNMes)₈ >99 90 Example 22

Co₂(CN^(t)Bu)₈ 60 52 Example 23

Co₂(CNAd)₈ >99 82 Comparative Example 4

Co₂(CO)₈ <1 <1

[4] Hydrosilane Reduction Reaction Using, as Substrate, Compound HavingCarbon-Oxygen Unsaturated Bond or Carbon-Nitrogen Unsaturated Bond[Example 24] Hydrosilane Reduction Reaction by Dimethylphenylsilane ofAcetophenone Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),acetophenone (120 mg, 1.0 mmol), and dimethylphenylsilane (177 mg, 1.3mmol) were added to a reactor, and stirring was performed at 50° C. for24 hours. After the reaction ended, ¹H-NMR spectrum was measured todetermine the structure and the yield of the product. The results areshown in Table 7.

¹H-NMR (400 MHz, CDCl₃):

0.28 (s, 3H), 0.33 (s, 3H), 1.42 (d, J=6.4 Hz), 4.85 (q, 6.4 Hz, 1H),7.16-7.41 (m, 8H), 7.53-7.59 (m, 2H).

[Example 25] Hydrosilane Reduction Reaction by1,1,3,3-Tetramethyldisiloxane of Acetophenone Using Fe(CN^(t)Bu)₅ asCatalyst

Fe(CN^(t)Bu)₅ obtained in Synthesis Example 4 (4.7 mg, 0.01 mmol),acetophenone (120 mg, 1.0 mmol), and 1,1,3,3-tetramethyldisiloxane (147mg, 1.3 mmol) were added to a reactor, and stirring was performed at 50°C. for 24 hours. After the reaction ended, ¹H-NMR spectrum was measuredto determine the structure and the yield of the product. The results areshown in Table 7.

1:1 adduct (a); ¹H-NMR (400 MHz, CDCl₃):

0.02 (s, 3H), 0.10 (s, 3H), 0.13 (d, J=3.0, 3H), 0.14 (d, J=3.0, 3H),1.46 (d, J=6.5 Hz, 3H), 4.66 (m, 1H), 4.98 (q, 6.4 Hz, 1H), 7.19-7.37(m, 5H).

1:2 adduct (b); ¹H-NMR (400 MHz, CDCl₃):

0.05-0.17 (m, 12H), 1.44 (d, J=6.5 Hz, 6H), 4.94 (q, 6.4 Hz, 2H),7.19-7.37 (m, 10H).

Comparative Example 5 Hydrosilane Reduction Reaction by1,1,3,3-Tetramethyldisiloxane of Acetophenone Using Fe₂(CO)₉ as Catalyst

Fe₂(CO)₅ (1.8 mg, 0.005 mmol), acetophenone (120 mg, 1.0 mmol), and1,1,3,3-tetramethyldisiloxane (147 mg, 1.3 mmol) were added to areactor, and stirring was performed at 50° C. for 24 hours. After thereaction ended, ¹H-NMR spectrum was measured to determine the structureand the yield of the product. The results are shown in Table 7.

TABLE 7 Yield Hydrosilane Structure of product Catalyst (%) Example 24dimethylphenylsilane

Co₂(CNAd)₈ >99 Example 25 1,1,3,3- tetramethyldisiloxane

Fe(CN^(t)Bu)₅   52 (a:b = 1:1) Comparative Example 5 1,1,3,3-tetramethyldisiloxane

Fe₂(CO)₉    8 (a:b = 3:1)

[Example 26] Hydrosilane Reduction Reaction by Diphenylsilane ofN,N-Dimethylbenzamide Using Co₂(CNMes)₈ as Catalyst

Co₂(CNMes)₈ obtained in Synthesis Example 3 (6.4 mg, 0.005 mmol),N,N-dimethylbenzamide (149 mg, 1.0 mmol), and diphenylsilane (239 mg,1.3 mmol) were added to a reactor, and stirring was performed at 50° C.for 24 hours. After the reaction ended, ¹H-NMR spectrum was measured todetermine the structure and the yield of the product. The results areshown in Table 8.

¹H-NMR (400 MHz, CDCl₃): 2.24 (s, 6H), 3.42 (s, 2H), 7.30-7.38 (m, 5H).

[Example 27] Hydrosilane Reduction Reaction by1,1,3,3-Tetramethyldisiloxane of N,N-Dimethylbenzamide UsingFe(CN^(t)Bu)₅ as Catalyst

Fe(CN^(t)Bu)₅ obtained in Synthesis Example 4 (4.7 mg, 0.01 mmol),N,N-dimethylbenzamide (149 mg, 1.0 mmol), and1,1,3,3-tetramethyldisiloxane (147 mg, 1.3 mmol) were added to areactor, and stirring was performed at 50° C. for 24 hours. After thereaction ended, ¹H-NMR spectrum was measured to determine the structureand the yield of the product. The results are shown in Table 8.

Comparative Example 6 Hydrosilane Reduction Reaction by Diphenylsilaneof N,N-Dimethylbenzamide Using Co₂(CO)₈ as Catalyst

Co₂(CO)₈ (1.7 mg, 0.005 mmol), N,N-dimethylbenzamide (149 mg, 1.0 mmol),and diphenylsilane (239 mg, 1.3 mmol) were added to a reactor, andstirring was performed at 50° C. for 24 hours. After the reaction ended,¹H-NMR spectrum was measured to determine the structure and the yield ofthe product. The results are shown in Table 8.

TABLE 8 Yield Hydrosilane Catalyst (%) Example 26 diphenylsilaneCo₂(CNMes)₈ 98 Example 27 1,1,3,3-tetramethyldisiloxane Fe(CN^(t)Bu)₅ 38Comparative diphenylsilane Co₂(CO)₈ 2 Example 6

[Example 28] Hydrosilane Reduction Reaction by1,1,3,3-Tetramethyldisiloxane of Acetonitrile Using Co₂(CN^(t)Bu)₈ asCatalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),acetonitrile (41 mg, 1.0 mmol), and 1,1,3,3-tetramethyldisiloxane (147mg, 1.3 mmol) were added to a reactor, and stirring was performed at 50°C. for 24 hours. After the reaction ended, a ¹H-NMR spectrum wasmeasured to determine the structure and the yield of the product. Theresults are shown in Table 9.

¹H-NMR (400 MHz, CDCl₃):

0.18 (s, 6H), 0.19 (s, 6H), 1.02 (t, J=6.4, 3H), 2.88 (q, J=6.4, 2H).

Comparative Example 7 Hydrosilane Reduction Reaction by1,1,3,3-Tetramethyldisiloxane of Acetonitrile Using Co₂(CO)₈ as Catalyst

Co₂(CO)₈ (1.7 mg, 0.005 mmol), acetonitrile (41 mg, 1.0 mmol), and1,1,3,3-tetramethyldisiloxane (147 mg, 1.3 mmol) were added to areactor, and stirring was performed at 50° C. for 24 hours. After thereaction ended, ¹H-NMR spectrum was measured to determine the structureand the yield of the product. The results are shown in Table 9.

TABLE 9 Yield Product Catalyst (%) Example 28

Co₂(CN^(t)Bu)₈ 98 Comparative Example 7

Co₂(CO)₈ <1

[5] Hydrogenation Reaction Using Compound Having Carbon-CarbonUnsaturated Bond as Substrate [Example 29] Hydrogenation Reaction of1-Octene Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (6.4 mg, 0.005 mmol) and1-octene (1.12 g, 10 mmol) were added to a reactor for an autoclave,hydrogen at 10 atm. was introduced, and stirring was performed at 80° C.for 24 hours. After the reaction ended, ¹H-NMR spectrum was measured todetermine the structure and the yield of the product. The results areshown in Table 10.

¹H-NMR (CDCl₃, 400 MHz): δ=0.88 (t, J=7.2 Hz, 6H), 1.16-1.36 (m, 12H).

[Example 30] Hydrogenation Reaction of Styrene Using Fe(CN^(t)Bu)₅ asCatalyst

Fe(CN^(t)Bu)₅ obtained in Synthesis Example 4 (4.7 mg, 0.01 mmol) andstyrene (1.04 g, 10 mmol) were added to a reactor for an autoclave,hydrogen at 10 atm. was introduced, and stirring was performed at 80° C.for 24 hours. After the reaction ended, ¹H-NMR spectrum was measured todetermine the structure and the yield of the product. The results areshown in Table 10.

¹H-NMR (CDCl₃, 400 MHz):

δ=1.13 (t, J=7.2 Hz, 3H), 2.54 (q, J=7.2 Hz, 2H), 7.02-7.20 (m, 5H).

TABLE 10 Yield Alkene Catalyst Product (%) TON Example 29 1-octeneCo₂(CN^(t)Bu)₈ octane >99 1,000 Example 30 styrene Fe(CN^(t)Bu)₅ ethylbenzene 22 220

[Example 31] Hydrosilylation Reaction by Triethylsilane ofα-Methylstyrene Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),α-methylstyrene (129 μL, 1.0 mmol), and triethylsilane (151 mg, 1.3mmol) were added to a reactor, and stirring was performed at 25° C. for24 hours. After the reaction ended, ¹H-NMR spectrum was measured todetermine the structure and the yield of the product. A multiplet of2.86 ppm in the desired product was observed, and the yield was found.The results are shown in Table 11.

¹H-NMR (396 MHz, CDCl₃) δ:

7.21-7.27 (m, 4H), 7.15-7.17 (m, 1H), 2.86 (sext, J=6.8, 1H), 1.27 (d,J=6.8, 3H), 0.98 (dd, J=14.8, 6.8 Hz, 1H),

0.90 (dd, J=14.8, 6.8 Hz, 1H), 0.86 (t, J=8.0, 9H), 0.34-0.48 (m, 6H).

[Example 32] Hydrosilylation Reaction by Dimethylphenylsilane ofα-Methylstyrene Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),α-methylstyrene (129 μL, 1.0 mmol), and dimethylphenylsilane (177 mg,1.3 mmol) were added to a reactor, and stirring was performed at 25° C.for 24 hours. After the reaction ended, ¹H-NMR spectrum was measured todetermine the structure and the yield of the product. A multiplet of2.85 ppm in the desired product was observed, and the yield was found.The results are shown in Table 11.

¹H-NMR (396 MHz, CDCl₃) δ:

7.44-7.47 (2H, m), 7.31-7.34 (3H, m), 7.21-7.26 (2H, m), 7.11-7.17 (3H,m), 2.85 (sext, J=6.8, 1H), 1.23 (d, J=6.8, 3H), 1.22 (dd, J=14.8, 6.8Hz, 1H), 1.15 (dd, J=14.8, 6.8 Hz, 1H), 0.15 (s, 3H), 0.09 (s, 3H).

TABLE 11 Conver- sion Yield Silane Catalyst (%) (%) Example 31triethylsilane Co₂(CN^(t)Bu)₈ >99 >99 Example 32 dimethylphenylsilaneCo₂(CN^(t)Bu)₈ >99 >99

[Example 33] Hydrosilylation Reaction by Polydimethylsiloxane Endblockedat Both Terminals by Dimethylhydrogensiloxy Groups of α-MethylstyreneUsing Co₂(CNAd)₈ as Catalyst

Co₂(CNAd)₈ obtained in Synthesis Example 2 (6.4 mg, 0.005 mmol),α-methylstyrene (1.53 mg, 13 mmol), and polydimethylsiloxane endblockedat both terminals by dimethylhydrogensiloxy groups (degree ofpolymerization 18) (7.4 g, 5.0 mmol) were added to a reactor, andstirring was performed at 50° C. for 24 hours. After the reaction ended,¹H-NMR spectrum was measured to determine the structure and the yield ofthe product. A multiplet at 0.98 ppm, which is a signal of protons oncarbon adjacent to silicon in the desired product, was observed, and theyield was found (yield >99%).

¹H-NMR (396 MHz, CDCl₃) δ:

7.27 (t, J=6.8, 2H), 7.21 (d, J=6.8, 2H), 7.15 (t, J=6.8, 1H), 2.92(sext, J=6.8, 1H), 1.28 (d, J=6.8, 3H), 0.90-0.98 (m, 2H), 0.05 (s),−0.05 (s), −0.07 (s).

[Example 34] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof α-Methylstyrene Using, as a Catalyst, Substance Obtained by AllowingCo₂(CNMes)₈ to Stand in Air for 24 Hours

Co₂(CNMes)₈ obtained in Synthesis Example 3 (6.4 mg, 0.005 mmol) wasadded to a reactor in a glove box. The reactor was taken out of theglove box, and was allowed to stand in air at room temperature for 24hours. After that, the reactor was brought into the glove box,α-methylstyrene (129 μL, 1.0 mmol) and 1,1,1,3,3-pentamethyldisiloxane(254 μL, 1.3 mmol) were added to the reactor, and stirring was performedat 25° C. for 24 hours. After the reaction ended, ¹H-NMR spectrum wasmeasured to determine the structure and the yield of the product. Amultiplet at 0.94 ppm, which is a signal of protons on carbon adjacentto silicon in the desired product, was observed, and the yield was found(yield >99%).

[Example 35] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof Styrene Using Fe(CNAd)₅ as Catalyst

Fe(CNAd)₅ obtained in Synthesis Example 5 (8.6 mg, 0.01 mmol), styrene(114 μL, 1.0 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3mmol) were added to a reactor, and stirring was performed at 50° C. for24 hours. After the reaction ended, ¹H-NMR spectrum was measured todetermine the structure and the yield of the product. A multiplet at0.90 ppm, which is a signal of protons on carbon adjacent to silicon inthe desired product, was observed, and the yield was found. The resultsare shown in Table 12.

[Example 36] Hydrosilylation Reaction by Diethoxy(Methyl)Silane ofStyrene Using Fe(CNAd)₅ as Catalyst

Fe(CNAd)₅ obtained in Synthesis Example 5 (8.6 mg, 0.01 mmol), styrene(114 μL, 1.0 mmol), and diethoxy(methyl)silane (175 mg, 1.3 mmol) wereadded to a reactor, and stirring was performed at 50° C. for 24 hours.After the reaction ended, ¹H-NMR spectrum was measured to determine thestructure and the yield of the product. A multiplet at 0.90 ppm, whichis a signal of protons on carbon adjacent to silicon in the desiredproduct, was observed, and the yield was found. The results are shown inTable 12.

¹H-NMR (396 MHz, CDCl₃) δ:

7.20 (m, 5H), 3.80 (m, 4H) 2.68-2.72 (m, 2H), 1.23 (t, J=6.8, 6H),0.97-1.01 (m, 2H), 0.12 (s, 3H).

TABLE 12 Conver- sion Yield Silane Catalyst (%) (%) Example 351,1,1,3,3- Fe(CNAd)₅ >99 >99 pentamethyldisiloxane Example 36diethoxy(methyl)silane Fe(CNAd)₅ >99 >99

[Example 37] Hydrosilylation Reaction by Polydimethylsiloxane Endblockedat Both Terminals by Dimethylhydrogensiloxy Groups of Styrene UsingFe(CNAd)₅ as Catalyst

Fe(CNAd)₅ obtained in Synthesis Example 5 (8.6 mg, 0.01 mmol), styrene(154 μL, 1.3 mmol), and polydimethylsiloxane endblocked at bothterminals by dimethylhydrogensiloxy groups (degree of polymerization 18)(0.74 g, 0.50 mmol) were added to a reactor, and stirring was performedat 50° C. for 24 hours. After the reaction ended, ¹H-NMR spectrum wasmeasured to determine the structure and the yield of the product. Amultiplet at 0.90 ppm, which is a signal of protons on carbon adjacentto silicon in the desired product, was observed, and the yield wasfound. The results are shown in Table 13.

¹H-NMR (396 MHz, CDCl₃) δ:

7.24-7.29 (m, 2H), 7.13-7.22 (m, 3H), 2.61-2.68 (m, 2H), 0.86-0.92 (m,2H), 0.08 (s), 0.07 (s).

TABLE 13 Conversion of Si—H Yield (%) (%) Example 37 >99 >99

[Example 38] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof Styrene Using Ni(CN^(t)Bu)₄ as Catalyst

Ni(CN^(t)Bu)₄ obtained in Synthesis Example 6 (3.9 mg, 0.01 mmol),styrene (114 μL, 0.01 mmol), and 1,1,1,3,3-pentamethyldisiloxane (254μL, 1.3 mmol) were added to a reactor, and stirring was performed at 80°C. for 24 hours. After the reaction ended, ¹H-NMR spectrum was measuredto determine the structure and the yield of the product. A multiplet at2.65 ppm, which is a signal of protons on carbon adjacent to silicon inthe desired product, was observed, and the yield was found (yield: 39%).

¹H-NMR (396 MHz, CDCl₃) δ:

7.22-7.29 (m, 5H), 2.65 (q, J=7.6 Hz, 1H), 1.35 (d, J=7.6 Hz, 2H), 0.01(s, 9H), −0.01 (s, 3H), −0.02 (s, 3H).

[Example 39] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof 1,1,1,3,3-Pentamethyl-3-Vinyldisiloxane Using Co₂(CNMes)₈ as Catalyst

Co₂(CNMes)₈ obtained in Synthesis Example 3 (6.4 mg, 0.005 mmol),1,1,1,3,3-pentamethyl-3-vinyldisiloxane (174 mg, 1.0 mmol), and1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) were added to areactor, and stirring was performed at 80° C. for 3 hours. After thereaction ended, ¹H-NMR spectrum was measured to determine the structureand the yield of the product. A multiplet at 0.40 ppm, which is a signalof protons on carbon adjacent to silicon in the desired product, wasobserved, and the yield was found. The results are shown in Table 14.

¹H-NMR (396 MHz, CDCl₃) δ: 0.03 (s, 12H), 0.06 (s, 18H), 0.40 (s, 4H).

[Example 40] Hydrosilylation Reaction by 1,1,1,3,3-Pentamethyldisiloxaneof Vinyltriethoxysilane Using Co₂(CN^(t)Bu)₈ as Catalyst

Co₂(CN^(t)Bu)₈ obtained in Synthesis Example 1 (3.4 mg, 0.005 mmol),vinyltriethoxysilane (190 mg, 1.0 mmol), and1,1,1,3,3-pentamethyldisiloxane (254 μL, 1.3 mmol) were added to areactor, and stirring was performed at 50° C. for 24 hours. After thereaction ended, ¹H-NMR spectrum was measured to determine the structureand the yield of the product. A multiplet at 0.50 ppm, which is a signalof protons on carbon adjacent to silicon in the desired product, wasobserved, and the yield was found. The results are shown in Table 14.

¹H-NMR (396 MHz, CDCl₃) δ:

3.78 (6H, q, J=7.0 Hz), 1.19 (9H, t, J=7.0 Hz), 0.47-0.53 (4H, m), 0.02(9H, s), 0.00 (6H, s).

TABLE 14 Conver- sion Yield Alkene Catalyst (%) (%) Example 391,1,1,3,3- Co₂(CNMes)₈ 83 30 pentamethyl- 3-vinyldisiloxane Example 40vinyltriethoxysilane Co₂(CN^(t)Bu)₈ >99 53

1. A catalyst comprising a compound represented by formula (1) below,and having activity in at least one reaction selected fromhydrosilylation reaction or hydrogenation reaction on an aliphaticunsaturated bond and hydrosilane reduction reaction on a carbon-oxygenunsaturated bond or a carbon-nitrogen unsaturated bond,M_(n)(L)_(m)  (1) wherein M represents Fe, Co, or Ni with an oxidationnumber of 0, L represents an isocyanide ligand represented by formula(2) below, n represents an integer of 1 to 8, and m represents aninteger of 2 to 12,(CN)_(x)—R¹  (2) wherein R¹ represents a monovalent to trivalent organicgroup that has 1 to 30 carbon atoms and is optionally substituted with ahalogen atom and in which one or more atoms selected from oxygen,nitrogen, sulfur, and silicon are optionally interposed, and xrepresents an integer of 1 to
 3. 2. The catalyst according to claim 1,wherein, in the formula (2), x is
 1. 3. The catalyst according to claim1, wherein, in the formula (1), when n=1, m=2, 4, or 5, when n=2 to 4,m=an integer of 6 to 10, and when n=8, m=12.
 4. The catalyst accordingto claim 1, wherein, in the formula (1), when M is Fe, n=1 and m=5, whenM is Co, n=2 and m=8, and when M is Ni, n=1 and m=2 or 4, or n=3, 4, or8 and m=4, 6, 7, or
 12. 5. The catalyst according to claim 1, wherein Min the formula (1) is Fe or Co.
 6. The catalyst according to claim 1,wherein R¹ in the formula (2) is a monovalent hydrocarbon group having 1to 30 carbon atoms.
 7. The catalyst according to claim 6, wherein R¹ inthe formula (2) is at least one hydrocarbon group selected from an alkylgroup having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20carbon atoms, an aryl group having 6 to 30 carbon atoms, and analkylaryl group having 7 to 30 carbon atoms.
 8. The catalyst accordingto claim 7, wherein R¹ in the formula (2) is at least one hydrocarbongroup selected from a t-butyl group, a 1-adamantyl group, a mesitylgroup, a phenyl group, a 2,6-dimethylphenyl group, and a2,6-diisopropylphenyl group.
 9. A method for producing a product ofhydrosilylation reaction between an aliphatic unsaturatedbond-containing compound and a Si—H bond-containing compound, whereinthe method uses the catalyst according to claim
 1. 10. A method forproducing a product of hydrogenation reaction of an aliphaticunsaturated bond-containing compound, wherein the method uses thecatalyst according to claim
 1. 11. The production method according toclaim 9, wherein the aliphatic unsaturated bond-containing compound isan olefin compound, or a silane compound or an organopolysiloxane havingan alkenyl group bonded to a Si atom.
 12. A method for producing aproduct of reduction reaction by a Si—H bond-containing compound of acompound having a carbon-oxygen unsaturated bond or a carbon-nitrogenunsaturated bond, wherein the method uses the catalyst according toclaim
 1. 13. The method for producing a product of reduction reactionaccording to claim 12, wherein the compound having a carbon-oxygenunsaturated bond or a carbon-nitrogen unsaturated bond is an aldehydecompound, a ketone compound, an amide compound, or a nitrile compound.